TWI658129B - Liquid crystal composition and use thereof, and liquid crystal display element - Google Patents
Liquid crystal composition and use thereof, and liquid crystal display element Download PDFInfo
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- TWI658129B TWI658129B TW103136560A TW103136560A TWI658129B TW I658129 B TWI658129 B TW I658129B TW 103136560 A TW103136560 A TW 103136560A TW 103136560 A TW103136560 A TW 103136560A TW I658129 B TWI658129 B TW I658129B
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- liquid crystal
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- phenylene
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- 239000000203 mixture Substances 0.000 title claims abstract description 170
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 126
- 150000001875 compounds Chemical class 0.000 claims abstract description 279
- -1 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene Chemical group 0.000 claims description 61
- 239000001257 hydrogen Substances 0.000 claims description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims description 57
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- 125000003342 alkenyl group Chemical group 0.000 claims description 45
- 125000000217 alkyl group Chemical group 0.000 claims description 45
- 239000011737 fluorine Substances 0.000 claims description 33
- 229910052731 fluorine Inorganic materials 0.000 claims description 33
- 229910052736 halogen Inorganic materials 0.000 claims description 33
- 150000002367 halogens Chemical group 0.000 claims description 32
- 125000003545 alkoxy group Chemical group 0.000 claims description 30
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 21
- 230000003287 optical effect Effects 0.000 claims description 20
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 12
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 9
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 claims description 9
- 125000005701 difluoromethyleneoxy group Chemical group FC(F)([*:1])O[*:2] 0.000 claims description 9
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 6
- 125000005449 2-fluoro-1,4-phenylene group Chemical group [H]C1=C([*:2])C([H])=C(F)C([*:1])=C1[H] 0.000 claims description 5
- 125000003302 alkenyloxy group Chemical class 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 125000005699 methyleneoxy group Chemical group [H]C([H])([*:1])O[*:2] 0.000 claims description 5
- 125000005714 2,5- (1,3-dioxanylene) group Chemical group [H]C1([H])OC([H])([*:1])OC([H])([H])C1([H])[*:2] 0.000 claims description 4
- 125000005453 2,5-difluoro-1,4-phenylene group Chemical group [H]C1=C([*:1])C(F)=C([H])C([*:2])=C1F 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims 5
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims 1
- 238000005452 bending Methods 0.000 claims 1
- 230000005684 electric field Effects 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000012071 phase Substances 0.000 description 36
- 238000005259 measurement Methods 0.000 description 20
- 0 *C(CC1)CCC1C(CC1)CCC1C=C* Chemical compound *C(CC1)CCC1C(CC1)CCC1C=C* 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000000654 additive Substances 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 150000002431 hydrogen Chemical group 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000002518 antifoaming agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000003505 polymerization initiator Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000006017 1-propenyl group Chemical group 0.000 description 3
- 239000004990 Smectic liquid crystal Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000006039 1-hexenyl group Chemical group 0.000 description 2
- 125000006023 1-pentenyl group Chemical group 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
- 125000006040 2-hexenyl group Chemical group 0.000 description 2
- 125000006024 2-pentenyl group Chemical group 0.000 description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 2
- 125000006041 3-hexenyl group Chemical group 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000013213 extrapolation Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- ZKJNETINGMOHJG-GGWOSOGESA-N (e)-1-[(e)-prop-1-enoxy]prop-1-ene Chemical compound C\C=C\O\C=C\C ZKJNETINGMOHJG-GGWOSOGESA-N 0.000 description 1
- HNEGJTWNOOWEMH-UHFFFAOYSA-N 1-fluoropropane Chemical group [CH2]CCF HNEGJTWNOOWEMH-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- 125000005450 2,3-difluoro-1,4-phenylene group Chemical group [H]C1=C([*:2])C(F)=C(F)C([*:1])=C1[H] 0.000 description 1
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- 125000005734 2-chloro-3-fluoro-1,4-phenylene group Chemical group [H]C1=C([H])C([*:1])=C(Cl)C(F)=C1[*:2] 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 229960002944 cyclofenil Drugs 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005446 heptyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
- C09K19/0208—Twisted Nematic (T.N.); Super Twisted Nematic (S.T.N.); Optical Mode Interference (O.M.I.)
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
- C09K19/0216—Super Birefringence Effect (S.B.E.); Electrically Controlled Birefringence (E.C.B.)
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/137—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0466—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the linking chain being a -CF2O- chain
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
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Abstract
本發明為一種液晶組成物、及含有該組成物的液晶顯示元件,所述液晶組成物含有具有大的正介電各向異性的特定化合物作為第一成分、及具有小的黏度的特定化合物作為第二成分,且亦可含有具有高的上限溫度或者小的黏度的特定化合物作為第三成分、具有大的正介電各向異性的特定化合物作為第四成分、或者具有負介電各向異性的特定化合物作為第五成分,並且所述液晶組成物具有向列相。 The invention is a liquid crystal composition and a liquid crystal display element containing the composition. The liquid crystal composition contains a specific compound having a large positive dielectric anisotropy as a first component and a specific compound having a small viscosity as a first component. The second component may also contain a specific compound having a high upper temperature or a small viscosity as the third component, a specific compound having a large positive dielectric anisotropy as the fourth component, or a negative dielectric anisotropy A specific compound is used as the fifth component, and the liquid crystal composition has a nematic phase.
Description
本發明是有關於一種液晶組成物、含有該組成物的液晶顯示元件等。尤其有關於介電各向異性為正的液晶組成物,以及含有該組成物且具有扭轉向列(twisted nematic,TN)、光學補償彎曲(optically compensated bend,OCB)、面內切換(in-plane switching,IPS)、邊緣場切換(fringe field switching,FFS)、或者電場感應光反應配向(field-induced photo-reactive alignment,FPA)的模式的主動矩陣(active matrix,AM)元件。 The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. In particular, it relates to a liquid crystal composition having a positive dielectric anisotropy, and a twisted nematic (TN), optically compensated bend (OCB), and in-plane containing the composition. Active matrix (AM) elements in switching (IPS), fringe field switching (FFS), or field-induced photo-reactive alignment (FPA) modes.
液晶顯示元件中,基於液晶分子的操作模式(operating mode)的分類為:相變(phase change,PC)、扭轉向列(twisted nematic,TN)、超扭轉向列(super twisted nematic,STN)、電控雙折射(electrically controlled birefringence,ECB)、光學補償彎曲(optically compensated bend,OCB)、面內切換(in-plane switching,IPS)、垂直配向(vertical alignment,VA)、邊緣場切 換(Fringe Field Switching,FFS)、電場感應光反應配向(field-induced photo-reactive alignment,FPA)等模式。基於元件的驅動方式的分類為被動矩陣(passive matrix,PM)與主動矩陣(active matrix,AM)。PM被分類為靜態式(static)與多工式(multiplex)等,AM被分類為薄膜電晶體(thin film transistor,TFT)、金屬-絕緣體-金屬(metal insulator metal,MIM)等。TFT的分類為非晶矽(amorphous silicon)以及多晶矽(polycrystal silicon)。後者根據製造步驟而分類為高溫型與低溫型。基於光源的分類為利用自然光的反射型、利用背光的透過型、以及利用自然光與背光的兩者的半透過型。 In liquid crystal display elements, the operating mode based on liquid crystal molecules is classified as: phase change (PC), twisted nematic (TN), super twisted nematic (STN), Electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (VA), fringe field cut (Fringe Field Switching (FFS), field-induced photo-reactive alignment (FPA) and other modes. The component-based driving methods are classified into a passive matrix (PM) and an active matrix (AM). PM is classified into static and multiplex, etc. AM is classified into thin film transistor (TFT), metal-insulator-metal (MIM), and the like. TFTs are classified into amorphous silicon and polycrystal silicon. The latter is classified into a high temperature type and a low temperature type according to manufacturing steps. The classification based on the light source is a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.
液晶顯示元件含有具有向列相的液晶組成物。該組成物具有適當的特性。藉由提高該組成物的特性,可獲得具有良好特性的AM元件。將兩者的特性中的關聯歸納於下述表1中。基於市售的AM元件來對組成物的特性進一步進行說明。向列相的溫度範圍與元件可使用的溫度範圍相關聯。向列相的較佳的上限溫度為約70℃以上,而且向列相的較佳的下限溫度為約-10℃以下。組成物的黏度與元件的響應時間相關聯。為了以元件顯示動態影像,較佳為響應時間短。理想為短於1毫秒的響應時間。因此,較佳為組成物的黏度小。更佳為低溫下的黏度小。組成物的彈性常數與元件的對比度相關聯。元件中,為了提高對比度,更佳為組成物的彈性常數大。 The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has appropriate characteristics. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The correlation between the characteristics of the two is summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase is related to the temperature range in which the element can be used. A preferred upper limit temperature of the nematic phase is about 70 ° C or higher, and a preferred lower limit temperature of the nematic phase is about -10 ° C or lower. The viscosity of a composition is related to the response time of the element. In order to display a moving image with a component, it is preferable that the response time is short. Ideally a response time shorter than 1 millisecond. Therefore, the viscosity of the composition is preferably small. More preferably, the viscosity is low at low temperatures. The elastic constant of the composition is related to the contrast of the device. In the device, in order to improve the contrast, it is more preferable that the composition has a large elastic constant.
組成物的光學各向異性與元件的對比度比相關聯。根據元件的模式而需要大的光學各向異性或者小的光學各向異性,即適當的光學各向異性。組成物的光學各向異性(△n)與元件的單元間隙(d)的積(△n×d)被設計成使對比度比為最大。適當的積的值依存於操作模式的種類。於TN之類的模式的元件中,適當的值為約0.45μm。該情況下,對單元間隙小的元件而言較佳為具有大的光學各向異性的組成物。組成物中的大的介電各向異性有助於元件中的低臨限電壓、小的消耗電力與大的對比度比。因此,較佳為大的介電各向異性。組成物中的大的比電阻有助於元件中的大的電壓保持率與大的對比度比。因此,較佳為在初始階段中不僅在室溫下,而且在接近於向列相的上限溫度的溫度下亦具有大的比電阻的組成物。較佳為在長時間使用後,不僅在室溫下,而且在接近於向列相的上限溫度的溫度下亦具有大的比電阻的組成物。組成物對紫外線及熱的穩定性與液晶顯示元件的壽命相關 聯。該些穩定性高時,該元件的壽命長。如上所述的特性對液晶投影機、液晶電視等中使用的AM元件而言較佳。 The optical anisotropy of the composition is related to the contrast ratio of the element. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy is required, that is, an appropriate optical anisotropy. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast ratio. The appropriate product value depends on the type of operation mode. In a device having a mode such as TN, a suitable value is about 0.45 μm. In this case, a composition having a large optical anisotropy is preferred for a device having a small cell gap. The large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption, and a large contrast ratio in the device. Therefore, a large dielectric anisotropy is preferred. A large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage is preferred. A composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after long-term use is preferred. The stability of the composition to ultraviolet rays and heat is related to the life of the liquid crystal display element Link. When the stability is high, the life of the element is long. The characteristics described above are preferable for AM elements used in liquid crystal projectors, liquid crystal televisions, and the like.
具有TN模式的AM元件中使用具有正的介電各向異性的組成物。具有VA模式的AM元件中使用具有負的介電各向異性的組成物。具有IPS模式或者FFS模式的AM元件中使用具有正或負的介電各向異性的組成物。聚合物穩定配向(PSA;polymer sustained alignment)型的AM元件中使用具有正或負的介電各向異性的組成物。具有正的介電各向異性的液晶組成物的例子揭示於如下的專利文獻1至專利文獻3中。 A composition having a positive dielectric anisotropy is used for an AM device having a TN mode. A composition having a negative dielectric anisotropy is used for an AM device having a VA mode. For an AM device having the IPS mode or the FFS mode, a composition having a positive or negative dielectric anisotropy is used. A polymer sustained alignment (PSA) type AM device uses a composition having a positive or negative dielectric anisotropy. Examples of the liquid crystal composition having positive dielectric anisotropy are disclosed in Patent Documents 1 to 3 below.
[現有技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利特開平7-2832號公報 [Patent Document 1] Japanese Patent Laid-Open No. 7-2832
[專利文獻2]日本專利特開平10-81679號公報 [Patent Document 2] Japanese Patent Laid-Open No. 10-81679
[專利文獻3]日本專利特開2008-69153號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2008-69153
本發明的其中一個目的為一種液晶組成物,其於向列相的高上限溫度、向列相的低下限溫度、小的黏度、適當的光學各向異性、大的介電各向異性、大的比電阻、對紫外線的高穩定性、對熱的高穩定性、大的彈性常數等特性中,滿足至少1種特性。另一目的為一種於至少2種特性之間具有適當平衡的液晶組成物。另一目的為一種含有此種組成物的液晶顯示元件。又一目的 為一種具有短的響應時間、大的電壓保持率、低的臨限電壓、大的對比度比、長的壽命等特性的AM元件。 One object of the present invention is a liquid crystal composition having a high upper limit temperature of a nematic phase, a low lower limit temperature of a nematic phase, a small viscosity, an appropriate optical anisotropy, a large dielectric anisotropy, Among the characteristics such as specific resistance, high stability to ultraviolet light, high stability to heat, and large elastic constant, at least one characteristic is satisfied. Another object is a liquid crystal composition having a suitable balance between at least two characteristics. Another object is a liquid crystal display element containing such a composition. Another purpose It is an AM device with characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long life.
本發明為一種液晶組成物、以及含有該組成物的液晶顯示元件,所述液晶組成物含有選自式(1)所表示的化合物的組群中的至少1種化合物作為第一成分、以及選自式(2)所表示的化合物的組群中的至少1種化合物作為第二成分,而且具有向列相。 The present invention is a liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (1) as a first component, and a liquid crystal display element containing the composition. At least one compound from the group of compounds represented by formula (2) is a second component and has a nematic phase.
式(1)及式(2)中,R1為碳數1至12的烷基、碳數1至12的烷氧基、或者碳數2至12的烯基;R2為碳數1至3的烷基或至少1個氫經鹵素所取代的碳數1至12的烷基;R3為氫或碳數1至5的烷基;環A及環B獨立地為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基、2,6-二氟-1,4-伸苯基、嘧啶-2,5-二基、1,3-二噁烷-2,5-二基、或者四氫吡喃-2,5-二基;Z1及Z2獨立地為單鍵、伸乙基、伸乙烯基、亞甲基氧基、羰基氧基、或者二氟亞甲基氧基;X1為氫或氟;Y1為氟、氯、至少1個氫經 鹵素所取代的碳數1至12的烷基、至少1個氫經鹵素所取代的碳數1至12的烷氧基、或者至少1個氫經鹵素所取代的碳數2至12的烯氧基;j及k獨立地為0、1、2或3;而且j與k的和為4以下。 In formulas (1) and (2), R 1 is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons; R 2 is 1 to 12 carbons Alkyl group 3 or at least 1 hydrogen substituted by alkyl group having 1 to 12 carbon atoms; R 3 is hydrogen or 1 to 5 carbon group; ring A and ring B are independently 1,4-end Cyclohexyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene Phenyl, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z 1 and Z 2 are independently a single bond , Ethylidene, vinylidene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy; X 1 is hydrogen or fluorine; Y 1 is fluorine, chlorine, and at least one hydrogen is replaced by halogen An alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms having at least one hydrogen substituted with halogen, or an alkenyl group having 2 to 12 carbon atoms having at least one hydrogen substituted with halogen; j And k are independently 0, 1, 2 or 3; and the sum of j and k is 4 or less.
本發明的優點為一種液晶組成物,其於向列相的高上限溫度、向列相的低下限溫度、小的黏度、適當的光學各向異性、大的介電各向異性、大的比電阻、對紫外線的高穩定性、對熱的高穩定性、大的彈性常數等特性中,滿足至少1種特性。另一優點為一種於至少2種特性之間具有適當平衡的液晶組成物。另一優點為一種含有此種組成物的液晶顯示元件。又一優點為一種具有短的響應時間、大的電壓保持率、低的臨限電壓、大的對比度比、長的壽命等特性的AM元件。 The invention has the advantages of a liquid crystal composition, which has a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, a small viscosity, an appropriate optical anisotropy, a large dielectric anisotropy, and a large ratio Among the characteristics such as resistance, high stability to ultraviolet light, high stability to heat, and large elastic constant, at least one characteristic is satisfied. Another advantage is a liquid crystal composition having a suitable balance between at least two characteristics. Another advantage is a liquid crystal display element containing such a composition. Still another advantage is an AM element having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, long lifetime, and the like.
該說明書中的用語的使用方法如下所述。有時將「液晶組成物」以及「液晶顯示元件」的用語分別簡稱為「組成物」以及「元件」。「液晶顯示元件」為液晶顯示面板以及液晶顯示模組的總稱。「液晶性化合物」是具有向列相、層列相(smectic phase)等液晶相的化合物,以及雖不具有液晶相,但出於調節向列相的溫度範圍、黏度、介電各向異性之類的特性的目的而混合於組成 物中的化合物的總稱。該化合物具有例如1,4-伸環己基或1,4-伸苯基之類的六員環,其分子結構為棒狀(rod like)。「聚合性化合物」是出於使組成物中生成聚合物的目的而添加的化合物。有時將選自式(1)所表示的化合物的組群中的至少1種化合物簡稱為「化合物(1)」。「化合物(1)」是指式(1)所表示的1種化合物或者2種以上的化合物。關於其他式所表示的化合物亦相同。與「經取代」相關的「至少1個」是指不僅對於位置可無限制地選擇,而且對於其個數亦可無限制地選擇。 The terms used in this specification are described below. The terms "liquid crystal composition" and "liquid crystal display element" may be simply referred to as "composition" and "element", respectively. "Liquid crystal display device" is a generic term for a liquid crystal display panel and a liquid crystal display module. A "liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a liquid crystal compound that does not have a liquid crystal phase, but is used to adjust the temperature range, viscosity, and dielectric anisotropy of the nematic phase Class properties are mixed in for the purpose of A general term for compounds in the substance. The compound has a six-membered ring such as 1,4-cyclohexyl or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. At least one compound selected from the group of compounds represented by formula (1) may be simply referred to as "compound (1)". "Compound (1)" means one compound or two or more compounds represented by formula (1). The same applies to compounds represented by other formulas. The "at least one" associated with "replaced" means that not only the position can be selected without limitation, but also the number of positions can be selected without limitation.
液晶組成物是藉由將多種液晶性化合物進行混合來製備。液晶性化合物的比例(含量)是由基於該液晶組成物的重量的重量百分率(重量%)所表示。於該組成物中視需要添加光學活性化合物、抗氧化劑、紫外線吸收劑、色素、消泡劑、聚合性化合物、聚合起始劑、聚合抑制劑之類的添加物。添加物的比例(添加量)是與液晶性化合物的比例同樣地,由基於液晶組成物的重量的重量百分率(重量%)所表示。有時亦使用重量百萬分率(ppm)。聚合起始劑以及聚合抑制劑的比例是例外地基於聚合性化合物的重量來表示。 The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. The ratio (content) of the liquid crystal compound is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition. To this composition, additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, and a polymerization inhibitor are added as needed. The ratio (addition amount) of the additive is the same as the ratio of the liquid crystal compound, and is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition. Sometimes parts per million by weight (ppm) is also used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.
有時將「向列相的上限溫度」簡稱為「上限溫度」。有時將「向列相的下限溫度」簡稱為「下限溫度」。「比電阻大」是指組成物在初始階段中不僅在室溫下,而且在接近於向列相的上限溫度的溫度下亦具有大的比電阻,並且在長時間使用後不僅在室溫下,而且在接近於向列相的上限溫度的溫度下亦具有大的比 電阻。「電壓保持率大」是指元件在初始階段中不僅在室溫下,而且在接近於向列相的上限溫度的溫度下亦具有大的電壓保持率,並且在長時間使用後不僅在室溫下,而且在接近於向列相的上限溫度的溫度下亦具有大的電壓保持率。 The "upper limit temperature of the nematic phase" may be simply referred to as the "upper limit temperature". The "lower limit temperature of the nematic phase" may be simply referred to as the "lower limit temperature". "High specific resistance" means that the composition has a large specific resistance not only at room temperature in the initial stage but also at a temperature close to the upper limit temperature of the nematic phase, and not only at room temperature after long-term use And has a large ratio at temperatures close to the upper limit of the nematic phase resistance. "Large voltage retention" means that the element has a large voltage retention not only at room temperature in the initial stage but also at a temperature close to the upper limit temperature of the nematic phase, and not only at room temperature after long-term use It also has a large voltage holding ratio at a temperature close to the upper limit temperature of the nematic phase.
「至少1個‘A’可經‘B’所取代」的表述是指‘A’的數量為任意。當‘A’的數量為1個時,‘A’的位置為任意,當‘A’的數量為2個以上時,它們的位置亦可無限制地選擇。該規則亦適用於「至少1個‘A’經‘B’所取代」的表述。 The expression "at least one 'A' may be replaced by 'B'" means that the number of 'A' is arbitrary. When the number of 'A' is one, the position of 'A' is arbitrary, and when the number of 'A' is two or more, their positions can also be selected without restriction. This rule also applies to the expression "at least 1 'A' replaced by 'B'".
成分化合物的化學式中,將末端基R1的記號用於多種化合物。該些化合物中,任意的2個R1所表示的2個基團可相同,或者亦可不同。例如,有化合物(1)的R1為乙基,且化合物(1-1)的R1為乙基的情況。亦有化合物(1)的R1為乙基,而化合物(1-1)的R1為丙基的情況。該規則亦適用於R4、X1等記號。式(1)中,當j為2時,存在2個環A。該化合物中,2個環A所表示的2個環可相同,或者亦可不同。當j大於2時,該規則亦適用於任意的2個環A。該規則亦適用於Z1、環B等。 In the chemical formula of the component compound, the symbol of the terminal group R 1 is used for various compounds. In these compounds, the two groups represented by arbitrary two R 1 may be the same or different. For example, there may be a case where R 1 of the compound (1) is an ethyl group and R 1 of the compound (1-1) is an ethyl group. In some cases, R 1 of the compound (1) is an ethyl group, and R 1 of the compound (1-1) is a propyl group. This rule also applies to symbols such as R 4 and X 1 . In formula (1), when j is 2, there are two rings A. In this compound, the two rings represented by the two rings A may be the same or different. When j is greater than 2, this rule also applies to any two rings A. This rule also applies to Z 1 , ring B, and so on.
2-氟-1,4-伸苯基是指下述的2個二價基。化學式中,氟可為朝左(L),亦可為朝右(R)。該規則亦適用於四氫吡喃-2,5-二基之類的非對稱的環的二價基。 2-Fluoro-1,4-phenylene refers to the two divalent groups described below. In the chemical formula, fluorine may be leftward (L) or rightward (R). This rule also applies to divalent radicals of asymmetric rings such as tetrahydropyran-2,5-diyl.
本發明為下述項等。 The present invention includes the following items.
項1. 一種液晶組成物,其含有選自式(1)所表示的化合物的組群中的至少1種化合物作為第一成分、以及選自式(2)所表示的化合物的組群中的至少1種化合物作為第二成分,而且具有向列相,
式(1)及式(2)中,R1為碳數1至12的烷基、碳數1至12的烷氧基、或者碳數2至12的烯基;R2為碳數1至3的烷基或至少1個氫經鹵素所取代的碳數1至12的烷基;R3為氫或碳數1至5的烷基;環A及環B獨立地為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基、2,6-二氟-1,4-伸苯基、嘧啶-2,5-二基、1,3-二噁烷-2,5-二基、或者四氫吡喃-2,5-二基;Z1及Z2獨立地為單鍵、伸乙基、伸乙烯基、亞甲基氧基、羰基氧基、 或者二氟亞甲基氧基;X1為氫或氟;Y1為氟、氯、至少1個氫經鹵素所取代的碳數1至12的烷基、至少1個氫經鹵素所取代的碳數1至12的烷氧基、或者至少1個氫經鹵素所取代的碳數2至12的烯氧基;j及k獨立地為0、1、2或3;而且j與k的和為4以下。 In formulas (1) and (2), R 1 is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons; R 2 is 1 to 12 carbons Alkyl group 3 or at least 1 hydrogen substituted by alkyl group having 1 to 12 carbon atoms; R 3 is hydrogen or 1 to 5 carbon group; ring A and ring B are independently 1,4-end Cyclohexyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene Phenyl, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; Z 1 and Z 2 are independently a single bond , Ethylidene, vinylidene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy; X 1 is hydrogen or fluorine; Y 1 is fluorine, chlorine, and at least one hydrogen is replaced by halogen An alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms having at least one hydrogen substituted with halogen, or an alkenyl group having 2 to 12 carbon atoms having at least one hydrogen substituted with halogen; j And k are independently 0, 1, 2 or 3; and the sum of j and k is 4 or less.
項2. 如項1所述的液晶組成物,其含有選自式(1-1)至式(1-12)所表示的化合物的組群中的至少1種化合物作為第一成分,
式(1-1)至式(1-12)中,R1為碳數1至12的烷基、碳數1至12的烷氧基、或者碳數2至12的烯基;X1、X2、X3、X4、X5、X6及X7獨立地為氫或氟;Y1為氟、氯、至少1個氫經鹵素所取代的碳數1至12的烷基、至少1個氫經鹵素所取代的碳數1至12的烷氧基、或者至少1個氫經鹵素所取代的碳數2至12的烯氧基。 In the formulae (1-1) to (1-12), R 1 is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms; X 1 , X 2 , X 3 , X 4 , X 5 , X 6, and X 7 are independently hydrogen or fluorine; Y 1 is fluorine, chlorine, at least one hydrogen is substituted with a halogen-containing alkyl group having 1 to 12 carbon atoms, at least An alkoxy group having 1 to 12 carbon atoms substituted by halogen with one hydrogen, or an alkoxy group having 2 to 12 carbon atoms substituted with at least one hydrogen substituted with halogen.
項3. 如項1或項2所述的液晶組成物,其中基於液晶組成物的重量,第一成分的比例為5重量%至40重量%的範圍,第二成分的比例為10重量%至60重量%的範圍。 Item 3. The liquid crystal composition according to Item 1 or 2, wherein the ratio of the first component is in a range of 5 to 40% by weight and the ratio of the second component is 10 to 10% by weight based on the weight of the liquid crystal composition. A range of 60% by weight.
項4. 如項1至項3中任一項所述的液晶組成物,其更含有選自式(3)所表示的化合物的組群中的至少1種化合物作為第三成分,
式(3)中,R4及R5獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、至少1個氫經鹵素所取代的碳數1至12的烷基、或者至少1個氫經氟所取代的碳數2至12的烯基;環C及環D獨立地為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、或者2,5-二氟-1,4-伸苯基;Z3為單鍵、伸乙基或者羰基氧基;n為1、2或3;此處,n為1時,環D為1,4-伸苯基。 In formula (3), R 4 and R 5 are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and at least one hydrogen is substituted with halogen Alkyl group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine; ring C and ring D are independently 1,4-cyclohexyl, 1,4-cyclo Phenyl, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z 3 is a single bond, ethylidene, or carbonyloxy; n is 1, 2 Or 3; here, when n is 1, ring D is 1,4-phenylene.
項5. 如項1至項4中任一項所述的液晶組成物,其含有選自式(3-1)至式(3-12)所表示的化合物的組群中的至少1種化合物作為第三成分,
式(3-1)至式(3-12)中,R4及R5獨立地為碳數1至12的 烷基、碳數1至12的烷氧基、碳數2至12的烯基、或者至少1個氫經氟所取代的碳數2至12的烯基。 In the formulae (3-1) to (3-12), R 4 and R 5 are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. Or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is replaced with fluorine.
項6. 如項4或項5所述的液晶組成物,其中基於液晶組成物的重量,第三成分的比例為5重量%至55重量%的範圍。 Item 6. The liquid crystal composition according to item 4 or item 5, wherein the proportion of the third component is in a range of 5 to 55% by weight based on the weight of the liquid crystal composition.
項7. 如項1至項6中任一項所述的液晶組成物,其更含有選自式(4)所表示的化合物的組群中的至少1種化合物作為第四成分,
式(4)中,R6為碳數1至12的烷基、碳數1至12的烷氧基、或者碳數2至12的烯基;環E為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基、2,6-二氟-1,4-伸苯基、嘧啶-2,5-二基、或者四氫吡喃-2,5-二基;Z4為單鍵、伸乙基、羰基氧基、或者二氟亞甲基氧基;X8及X9獨立地為氫或氟;Y2為氟、氯、至少1個氫經鹵素所取代的碳數1至12的烷基、至少1個氫經鹵素所取代的碳數1至12的烷氧基、或者至少1個氫經鹵素所取代的碳數2至12的烯氧基;p為1、2、3或4。 In formula (4), R 6 is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons; ring E is 1,4-cyclohexyl, 1 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine -2,5-diyl, or tetrahydropyran-2,5-diyl; Z 4 is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy; X 8 and X 9 are independent Ground is hydrogen or fluorine; Y 2 is fluorine, chlorine, at least one hydrogen alkyl group having 1 to 12 carbon atoms substituted with halogen, at least one hydrogen substituted alkyl group with 1 to 12 carbon atoms halogen, Or an alkenyl group having 2 to 12 carbons with at least one hydrogen substituted with halogen; p is 1, 2, 3, or 4.
項8. 如項1至項7中任一項所述的液晶組成物,其含有選自式(4-1)至式(4-24)所表示的化合物的組群中的至少1種化合物作為第四成分,
式(4-1)至式(4-24)中,R6為碳數1至12的烷基、碳數1至12的烷氧基、或者碳數2至12的烯基。 In the formulae (4-1) to (4-24), R 6 is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons.
項9. 如項7或項8所述的液晶組成物,其中基於液晶組成物的重量,第四成分的比例為5重量%至35重量%的範圍。 Item 9. The liquid crystal composition according to item 7 or item 8, wherein the proportion of the fourth component is in the range of 5% to 35% by weight based on the weight of the liquid crystal composition.
項10. 如項1至項9中任一項所述的液晶組成物,其含有選自式(5)所表示的化合物的組群中的至少1種化合物作為第五成分,
式(5)中,R7及R8獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、碳數2至12的烯氧基、或者至少1個氫經鹵素所取代的碳數1至12的烷基;環F及環I獨立地為1,4-伸環己基、1,4-伸環己烯基(1,4-cyclohexenylene)、1,4-伸苯基、至少1個氫經氟或氯所取代的1,4-伸苯基、或者四氫吡喃-2,5-二基;環G為2,3-二氟-1,4-伸苯基、2-氯-3-氟-1,4-伸苯基、2,3-二氟-5-甲基-1,4-伸苯基、3,4,5-三氟萘-2,6-二基、或者7,8-二氟色原烷-2,6-二基(7,8-difluorochromane-2,6-diyl);Z5及Z6獨立地為單鍵、伸乙基、羰基氧基、或者亞甲基氧基;e為1、2或3,f為0或1;而且e與f之和為3以下。 In formula (5), R 7 and R 8 are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. Or at least one hydrogen substituted alkyl group having 1 to 12 carbon atoms; ring F and ring I are independently 1,4-cyclohexyl, 1,4-cyclohexenyl (1,4 -cyclohexenylene), 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted by fluorine or chlorine, or tetrahydropyran-2,5-diyl; ring G is 2,3 -Difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3, 4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochromane-2,6-diyl (7,8-difluorochromane-2,6-diyl); Z 5 and Z 6 is independently a single bond, an ethylidene group, a carbonyloxy group, or a methyleneoxy group; e is 1, 2 or 3; f is 0 or 1; and the sum of e and f is 3 or less.
項11. 如項1至項10中任一項所述的液晶組成物,其含有選自式(5-1)至式(5-19)所表示的化合物的組群中的至少1種化合物作為第五成分,
式(5-1)至式(5-19)中,R7及R8獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、碳數2至12的烯氧基、或者至少1個氫經鹵素所取代的碳數1至12的烷基。 In the formulae (5-1) to (5-19), R 7 and R 8 are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. , An alkenyloxy group having 2 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is replaced with halogen.
項12. 如項10或項11所述的液晶組成物,其中基於液晶組成物的重量,第五成分的比例為3重量%至25重量%的範圍。 Item 12. The liquid crystal composition according to item 10 or item 11, wherein the proportion of the fifth component is in a range of 3% by weight to 25% by weight based on the weight of the liquid crystal composition.
項13. 如項1至項12中任一項所述的液晶組成物,其向列相的上限溫度為70℃以上,波長589nm下的光學各向異性(於25℃下測定)為0.07以上,而且頻率1kHz下的介電各向異性(於25℃下測定)為2以上。 Item 13. The liquid crystal composition according to any one of Items 1 to 12, wherein the upper limit temperature of the nematic phase is 70 ° C. or higher, and the optical anisotropy (measured at 25 ° C.) at a wavelength of 589 nm is 0.07 or higher. The dielectric anisotropy (measured at 25 ° C) at a frequency of 1 kHz is 2 or more.
項14. 一種液晶顯示元件,其含有如項1至項13中任一項所述的液晶組成物。 Item 14. A liquid crystal display element comprising the liquid crystal composition according to any one of Items 1 to 13.
項15. 如項14所述的液晶顯示元件,其中液晶顯示元件的操作模式為TN模式、ECB模式、OCB模式、IPS模式、FFS模式、或者FPA模式,液晶顯示元件的驅動方式為主動矩陣方式。 Item 15. The liquid crystal display element according to item 14, wherein the operation mode of the liquid crystal display element is TN mode, ECB mode, OCB mode, IPS mode, FFS mode, or FPA mode, and the driving mode of the liquid crystal display element is an active matrix method. .
項16. 一種如項1至項13中任一項所述的液晶組成物的用途,其用於液晶顯示元件中。 Item 16. The use of the liquid crystal composition according to any one of Items 1 to 13, which is used in a liquid crystal display element.
本發明還包括以下各項。(a)所述組成物,其更含有光學活性化合物、抗氧化劑、紫外線吸收劑、色素、消泡劑、聚合性化合物、聚合起始劑、聚合抑制劑等添加物的至少1種。(b)一種AM元件,其含有所述組成物。(c)更含有聚合性化合物的所述組成物、以及含有該組成物的聚合物穩定配向(PSA)型AM元件。(d)一種聚合物穩定配向(PSA)型的AM元件,其含有所述組成物,且該組成物中的聚合性化合物進行聚合。(e)一種元件,其含有所述組成物,而且具有PC、TN、STN、ECB、OCB、IPS、VA、FFS、或者FPA的模式。(f)一種透過型元件,其含有 所述組成物。(g)將所述組成物用作具有向列相的組成物的用途。(h)藉由在所述組成物中添加光學活性化合物而作為光學活性組成物的用途。 The present invention also includes the following items. (a) The composition further contains at least one of additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, and a polymerization inhibitor. (b) An AM device containing the composition. (c) The composition further containing a polymerizable compound, and a polymer stable alignment (PSA) type AM device containing the composition. (d) A polymer stabilized alignment (PSA) type AM device containing the composition and polymerizing a polymerizable compound in the composition. (e) An element containing the composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (f) a transmissive element containing The composition. (g) Use of the composition as a composition having a nematic phase. (h) Use as an optically active composition by adding an optically active compound to the composition.
以如下順序對本發明的組成物進行說明。第一,對組成物中的成分化合物的構成進行說明。第二,對成分化合物的主要特性、以及該化合物給組成物帶來的主要效果進行說明。第三,對組成物中的成分的組合、成分的較佳比例以及其根據進行說明。第四,對成分化合物的較佳形態進行說明。第五,示出較佳的成分化合物。第六,對可添加於組成物中的添加物進行說明。第七,對成分化合物的合成方法進行說明。最後,對組成物的用途進行說明。 The composition of the present invention will be described in the following order. First, the constitution of the component compounds in the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition will be described. Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. Fourth, preferred embodiments of the component compounds will be described. Fifth, preferred component compounds are shown. Sixth, additives that can be added to the composition will be described. Seventh, a method for synthesizing the component compounds will be described. Finally, the use of the composition will be described.
第一,對組成物中的成分化合物的構成進行說明。本發明的組成物被分類為組成物A及組成物B。組成物A除了含有選自化合物(1)、化合物(2)、化合物(3)、化合物(4)、及化合物(5)中的液晶性化合物以外,亦可更含有其他的液晶性化合物、添加物等。「其他的液晶性化合物」是與化合物(1)、化合物(2)、化合物(3)、化合物(4)、及化合物(5)不同的液晶性化合物。此種化合物是出於進一步調整特性的目的而混合於組成物中。添加物為光學活性化合物、抗氧化劑、紫外線吸收劑、色素、消泡劑、聚合性化合物、聚合起始劑、聚合抑制劑等。 First, the constitution of the component compounds in the composition will be described. The composition of the present invention is classified into a composition A and a composition B. The composition A contains a liquid crystal compound selected from the compound (1), the compound (2), the compound (3), the compound (4), and the compound (5), and may further contain other liquid crystal compounds and additives. Things. The "other liquid crystal compound" is a liquid crystal compound different from the compound (1), the compound (2), the compound (3), the compound (4), and the compound (5). Such a compound is mixed in the composition for the purpose of further adjusting the characteristics. The additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and the like.
組成物B實質上僅包含選自化合物(1)、化合物(2)、化合物(3)、化合物(4)、及化合物(5)中的液晶性化合物。「實 質上」是指組成物雖可含有添加物,但不含其他的液晶性化合物。與組成物A相比較,組成物B的成分的數量少。就降低成本的觀點而言,組成物B優於組成物A。就可藉由混合其他的液晶性化合物來進一步調整特性的觀點而言,組成物A優於組成物B。 Composition B contains substantially only a liquid crystal compound selected from the group consisting of compound (1), compound (2), compound (3), compound (4), and compound (5). "real By "qualitatively" it is meant that the composition may contain additives, but does not contain other liquid crystal compounds. Compared with composition A, the number of components of composition B is small. From the viewpoint of cost reduction, the composition B is superior to the composition A. From the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds, the composition A is superior to the composition B.
第二,對成分化合物的主要特性、以及該化合物給組成物的特性帶來的主要效果進行說明。基於本發明的效果,將成分化合物的主要特性歸納於表2中。表2的記號中,L是指大或高,M是指中等程度的,S是指小或低。記號L、M、S是基於成分化合物之間的定性比較的分類,0(零)是指值為零,或者接近零。 Second, the main characteristics of the component compounds and the main effects of the compounds on the characteristics of the composition will be described. Based on the effects of the present invention, the main characteristics of the component compounds are summarized in Table 2. In the symbols in Table 2, L is large or high, M is medium, and S is small or low. Symbols L, M, and S are classifications based on a qualitative comparison between component compounds, and 0 (zero) means that the value is zero, or close to zero.
當將成分化合物混合於組成物中時,成分化合物給組成物的特性帶來的主要效果如下所述。化合物(1)提高介電各向異性。化合物(2)降低黏度。化合物(3)提高上限溫度,或者降低下限溫度。化合物(4)降低下限溫度,而且提高介電各向異性。化合物(5)提高短軸方向的介電常數。 When the component compounds are mixed in the composition, the main effects of the component compounds on the characteristics of the composition are as follows. The compound (1) improves the dielectric anisotropy. Compound (2) reduces viscosity. The compound (3) raises the upper limit temperature or lowers the lower limit temperature. The compound (4) lowers the lower limit temperature and increases the dielectric anisotropy. The compound (5) increases the dielectric constant in the minor axis direction.
第三,對組成物中的成分的組合、成分化合物的較佳比 例及其根據進行說明。組成物中的成分的組合為:第一成分+第二成分、第一成分+第二成分+第三成分、第一成分+第二成分+第四成分、第一成分+第二成分+第三成分+第四成分、第一成分+第二成分+第五成分、第一成分+第二成分+第三成分+第五成分、第一成分+第二成分+第四成分+第五成分、或者第一成分+第二成分+第三成分+第四成分+第五成分。組成物中的成分的較佳組合為第一成分+第二成分+第三成分或者第一成分+第二成分+第三成分+第四成分。 Third, the combination of the components in the composition and the preferred ratio of the component compounds The example and its basis will be explained. The combination of the components in the composition is: the first component + the second component, the first component + the second component + the third component, the first component + the second component + the fourth component, the first component + the second component + the first component Three components + fourth component, first component + second component + fifth component, first component + second component + third component + fifth component, first component + second component + fourth component + fifth component Or the first component + the second component + the third component + the fourth component + the fifth component. A preferred combination of the components in the composition is a first component + a second component + a third component or a first component + a second component + a third component + a fourth component.
為了提高介電各向異性,第一成分的較佳比例為約5重量%以上,為了降低下限溫度,或者為了降低黏度,第一成分的較佳比例為約40重量%以下。尤佳的比例為約5重量%至約30重量%的範圍。特佳的比例為約5重量%至約25重量%的範圍。 In order to improve the dielectric anisotropy, the preferred ratio of the first component is about 5 wt% or more. In order to lower the lower limit temperature or to reduce the viscosity, the preferred ratio of the first component is about 40 wt% or less. A particularly preferred ratio is in the range of about 5% to about 30% by weight. A particularly preferred ratio is in the range of about 5 wt% to about 25 wt%.
為了降低黏度,第二成分的較佳比例為約10重量%以上,為了提高介電各向異性,第二成分的較佳比例為約60重量%以下。尤佳的比例為約15重量%至約55重量%的範圍。特佳的比例為約20重量%至約50重量%的範圍。 In order to reduce the viscosity, the preferred ratio of the second component is about 10% by weight or more. In order to improve the dielectric anisotropy, the preferred ratio of the second component is about 60% by weight or less. A particularly preferred ratio is in the range of about 15% by weight to about 55% by weight. A particularly preferred ratio is in the range of about 20% by weight to about 50% by weight.
為了提高上限溫度,或者為了降低黏度,第三成分的較佳比例為約5重量%以上,為了提高介電各向異性,第三成分的較佳比例為約55重量%以下。尤佳的比例為約10重量%至約50重量%的範圍。特佳的比例為約15重量%至約45重量%的範圍。 In order to increase the upper limit temperature, or to reduce the viscosity, the preferred ratio of the third component is about 5% by weight or more, and to improve the dielectric anisotropy, the preferred ratio of the third component is about 55% by weight or less. A particularly preferred ratio is in the range of about 10% by weight to about 50% by weight. A particularly preferred ratio is in the range of about 15% by weight to about 45% by weight.
為了提高介電各向異性,第四成分的較佳比例為約5重量%以上,為了降低下限溫度,第四成分的較佳比例為約35重量 %以下。尤佳的比例為約5重量%至約30重量%的範圍。特佳的比例為約5重量%至約25重量%的範圍。 In order to improve the dielectric anisotropy, the preferred ratio of the fourth component is about 5% by weight or more. In order to lower the lower limit temperature, the preferred ratio of the fourth component is about 35% by weight. %the following. A particularly preferred ratio is in the range of about 5% to about 30% by weight. A particularly preferred ratio is in the range of about 5 wt% to about 25 wt%.
為了提高介電各向異性,第五成分的較佳比例為約3重量%以上,為了降低下限溫度,第五成分的較佳比例為約25重量%以下。尤佳的比例為約5重量%至約20重量%的範圍。特佳的比例為約5重量%至約15重量%的範圍。 In order to improve the dielectric anisotropy, the preferred ratio of the fifth component is about 3% by weight or more. In order to lower the lower limit temperature, the preferred ratio of the fifth component is about 25% by weight or less. A particularly preferred ratio is in the range of about 5% to about 20% by weight. A particularly preferred ratio is in the range of about 5 wt% to about 15 wt%.
第四,對成分化合物的較佳形態進行說明。R1及R6獨立地為碳數1至12的烷基、碳數1至12的烷氧基、或者碳數2至12的烯基。為了提高對紫外線或熱的穩定性,較佳的R1或R6為碳數1至12的烷基。R2為碳數1至3的烷基或者至少1個氫經鹵素所取代的碳數1至12的烷基。較佳的R2為丙基或3-氟丙基。-CH=CH-R2中的-CH=CH-的立體構型有反式構型及順式構型,較佳為反式構型。R3為氫或碳數1至5的烷基。較佳的R3為氫或甲基。R4及R5獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、至少1個氫經鹵素所取代的碳數1至12的烷基、或者至少1個氫經氟所取代的碳數2至12的烯基。為了提高對紫外線或熱的穩定性等,較佳的R4或R5為碳數1至12的烷基,為了降低下限溫度,或者為了降低黏度,較佳的R4或R5為碳數2至12的烯基。R7及R8獨立地為碳數1至12的烷基、碳數1至12的烷氧基、碳數2至12的烯基、碳數2至12的烯氧基、或者至少1個氫經鹵素所取代的碳數1至12的烷基。為了提高穩定性,較佳的R7或R8為碳數1至12的烷基,為了提高介電各向異 性,較佳的R7或R8為碳數1至12的烷氧基。較佳的鹵素為氟或氯,尤佳的鹵素為氟。 Fourth, preferred embodiments of the component compounds will be described. R 1 and R 6 are independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons. In order to improve the stability to ultraviolet rays or heat, preferred R 1 or R 6 is an alkyl group having 1 to 12 carbon atoms. R 2 is an alkyl group having 1 to 3 carbons or an alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced with halogen. Preferred R 2 is propyl or 3-fluoropropyl. The three-dimensional configuration of -CH = CH- in -CH = CH-R 2 includes a trans configuration and a cis configuration, and a trans configuration is preferred. R 3 is hydrogen or an alkyl group having 1 to 5 carbon atoms. Preferred R 3 is hydrogen or methyl. R 4 and R 5 are independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, and at least 1 hydrogen having 1 to 12 carbon atoms substituted with halogen Alkyl, or at least 1 hydrogen alkenyl having 2 to 12 carbon atoms substituted with fluorine. In order to improve the stability to ultraviolet rays or heat, etc., a preferred R 4 or R 5 is an alkyl group having 1 to 12 carbon atoms. In order to lower the lower limit temperature or to reduce viscosity, a preferred R 4 or R 5 is a carbon number. 2 to 12 alkenyl. R 7 and R 8 are independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, an alkenyl group having 2 to 12 carbons, or at least one Alkyl having 1 to 12 carbons substituted by hydrogen with halogen. In order to improve stability, preferred R 7 or R 8 is an alkyl group having 1 to 12 carbons, and in order to improve dielectric anisotropy, preferred R 7 or R 8 is an alkoxy group having 1 to 12 carbons. The preferred halogen is fluorine or chlorine, and the more preferred halogen is fluorine.
較佳的烷基為:甲基、乙基、丙基、丁基、戊基、己基、庚基、或者辛基。為了降低黏度,尤佳的烷基為乙基、丙基、丁基、戊基、或者庚基。 Preferred alkyl groups are: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. To reduce viscosity, particularly preferred alkyl groups are ethyl, propyl, butyl, pentyl, or heptyl.
較佳的烷氧基為:甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基、或者庚氧基。為了降低黏度,尤佳的烷氧基為甲氧基或者乙氧基。 Preferred alkoxy groups are: methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, or heptyloxy. To reduce viscosity, a particularly preferred alkoxy group is methoxy or ethoxy.
較佳的烯基為:乙烯基、1-丙烯基、2-丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-戊烯基、2-戊烯基、3-戊烯基、4-戊烯基、1-己烯基、2-己烯基、3-己烯基、4-己烯基、或者5-己烯基。為了降低黏度,尤佳的烯基為乙烯基、1-丙烯基、3-丁烯基或3-戊烯基。該些烯基中的-CH=CH-的較佳立體構型依存於雙鍵的位置。出於為了降低黏度等原因,於1-丙烯基、1-丁烯基、1-戊烯基、1-己烯基、3-戊烯基、3-己烯基之類的烯基中較佳為反式構型。於2-丁烯基、2-戊烯基、2-己烯基之類的烯基中較佳為順式構型。該些烯基中,直鏈的烯基優於分支的烯基。 Preferred alkenyls are: vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. To reduce viscosity, particularly preferred alkenyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl. The preferred stereo configuration of -CH = CH- in these alkenyl groups depends on the position of the double bond. For reasons such as reducing viscosity, it compares with alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl. It is preferably a trans configuration. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl, the cis configuration is preferred. Among these alkenyl groups, linear alkenyl groups are superior to branched alkenyl groups.
至少1個氫經氟所取代的烯基的較佳例為:2,2-二氟乙烯基、3,3-二氟-2-丙烯基、4,4-二氟-3-丁烯基、5,5-二氟-4-戊烯基、或者6,6-二氟-5-己烯基。為了降低黏度,尤佳例為2,2-二氟乙烯基或者4,4-二氟-3-丁烯基。 Preferred examples of alkenyl in which at least one hydrogen is replaced by fluorine are: 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl , 5,5-difluoro-4-pentenyl, or 6,6-difluoro-5-hexenyl. In order to reduce the viscosity, a particularly preferred example is 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.
j及k獨立地為0、1、2或3,而且j與k的和為4以下。 為了降低下限溫度,較佳的j為0。為了提高上限溫度,較佳的k為1或2。n為1、2或3。為了降低下限溫度,較佳的n為2。p為1、2、3或4。為了降低下限溫度,較佳的p為2,為了提高介電各向異性,較佳的p為3。e為1、2或3,f為0或1,而且e與f的和為3以下。為了降低黏度,較佳的e為1,為了提高上限溫度,較佳的e為2或3。為了降低黏度,較佳的f為0,為了降低下限溫度,較佳的f為1。 j and k are independently 0, 1, 2 or 3, and the sum of j and k is 4 or less. In order to lower the lower limit temperature, preferably j is 0. In order to increase the upper limit temperature, k is preferably 1 or 2. n is 1, 2 or 3. In order to lower the lower limit temperature, the preferred n is two. p is 1, 2, 3, or 4. In order to lower the lower limit temperature, a preferred p is 2 and in order to increase the dielectric anisotropy, a preferred p is 3. e is 1, 2 or 3, f is 0 or 1, and the sum of e and f is 3 or less. In order to reduce the viscosity, the preferred e is 1, and in order to increase the upper limit temperature, the preferred e is 2 or 3. In order to reduce the viscosity, the preferred f is 0, and to lower the lower limit temperature, the preferred f is 1.
Z1及Z2獨立地為單鍵、伸乙基、伸乙烯基、亞甲基氧基、羰基氧基、或者二氟亞甲基氧基。為了降低黏度,較佳的Z1或Z2為單鍵,為了提高介電各向異性,較佳的Z1或Z2為二氟亞甲基氧基。Z3為單鍵、伸乙基或羰基氧基。為了降低黏度,較佳的Z3為單鍵。Z4為單鍵、伸乙基、羰基氧基、或者二氟亞甲基氧基。為了提高介電各向異性,較佳的Z4為二氟亞甲基氧基。Z5及Z6獨立地為單鍵、伸乙基、羰基氧基、或者亞甲基氧基。為了降低黏度,較佳的Z5或Z6為單鍵,為了提高介電各向異性,較佳的Z5或Z6為亞甲基氧基。 Z 1 and Z 2 are independently a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy, or difluoromethyleneoxy. In order to reduce the viscosity, the preferred Z 1 or Z 2 is a single bond. In order to improve the dielectric anisotropy, the preferred Z 1 or Z 2 is a difluoromethyleneoxy group. Z 3 is a single bond, ethylene or carbonyloxy. To reduce viscosity, the preferred Z 3 is a single bond. Z 4 is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy. To increase the dielectric anisotropy, the preferred Z 4 is difluoromethyleneoxy. Z 5 and Z 6 are independently a single bond, ethylene, carbonyloxy, or methyleneoxy. In order to reduce the viscosity, the preferred Z 5 or Z 6 is a single bond. In order to improve the dielectric anisotropy, the preferred Z 5 or Z 6 is a methyleneoxy group.
環A及環B獨立地為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基、2,6-二氟-1,4-伸苯基、嘧啶-2,5-二基、1,3-二噁烷-2,5-二基、或者四氫吡喃-2,5-二基。為了提高光學各向異性,較佳的環A或環B為1,4-伸苯基或者2-氟-1,4-伸苯基。環C及環D獨立地為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、或者2,5-二氟-1,4-伸苯基,n為1時,環D為1,4-伸苯基。 為了降低黏度,較佳的環C或環D為1,4-伸環己基,或者為了提高光學各向異性,較佳的環C或環D為1,4-伸苯基。環E為1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基、2,6-二氟-1,4-伸苯基、嘧啶-2,5-二基、或者四氫吡喃-2,5-二基。為了提高光學各向異性,較佳的環E為1,4-伸苯基或2-氟-1,4-伸苯基。環F及環I獨立地為1,4-伸環己基、1,4-伸環己烯基、1,4-伸苯基、至少1個氫經氟或氯所取代的1,4-伸苯基、或者四氫吡喃-2,5-二基。「至少1個氫經氟或氯所取代的1,4-伸苯基」的較佳例為2-氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基或2-氯-3-氟-1,4-伸苯基。為了降低黏度,較佳的環F或環I為1,4-伸環己基,為了提高介電各向異性,較佳的環F或環I為四氫吡喃-2,5-二基,為了提高光學各向異性,較佳的環F或環I為1,4-伸苯基。環G為2,3-二氟-1,4-伸苯基、2-氯-3-氟-1,4-伸苯基、2,3-二氟-5-甲基-1,4-伸苯基、3,4,5-三氟萘-2,6-二基、或者7,8-二氟色原烷-2,6-二基。為了提高介電各向異性,較佳的環G為2,3-二氟-1,4-伸苯基。為了提高上限溫度,與1,4-伸環己基有關的立體構型為反式構型優於順式構型。四氫吡喃-2,5-二基為或者,較佳為。 Ring A and Ring B are independently 1,4-cyclohexyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene , 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5- Second base. In order to improve optical anisotropy, the preferred ring A or ring B is 1,4-phenylene or 2-fluoro-1,4-phenylene. Ring C and Ring D are independently 1,4-cyclohexyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene When n is 1, ring D is 1,4-phenylene. In order to reduce the viscosity, the preferred ring C or ring D is 1,4-cyclohexyl, or in order to improve the optical anisotropy, the preferred ring C or ring D is 1,4-phenylene. Ring E is 1,4-cyclohexyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6- Difluoro-1,4-phenylene, pyrimidine-2,5-diyl, or tetrahydropyran-2,5-diyl. To improve optical anisotropy, the preferred ring E is 1,4-phenylene or 2-fluoro-1,4-phenylene. Ring F and Ring I are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenyl, at least one hydrogen substituted by fluorine or chlorine Phenyl, or tetrahydropyran-2,5-diyl. Preferred examples of "at least one hydrogen substituted by 1,4-phenylene with fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene Or 2-chloro-3-fluoro-1,4-phenylene. In order to reduce the viscosity, the preferred ring F or ring I is 1,4-cyclohexyl. In order to improve the dielectric anisotropy, the preferred ring F or ring I is tetrahydropyran-2,5-diyl. In order to improve optical anisotropy, the preferred ring F or ring I is 1,4-phenylene. Ring G is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4- Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochromogen-2,6-diyl. To increase the dielectric anisotropy, the preferred ring G is 2,3-difluoro-1,4-phenylene. In order to increase the upper limit temperature, the stereo configuration related to 1,4-cyclohexyl is a trans configuration rather than a cis configuration. Tetrahydropyran-2,5-diyl is or , Preferably .
X1、X2、X3、X4、X5、X6、X7、X8及X9獨立地為氫或 氟。為了提高介電各向異性,較佳的X1、X2、X3、X4、X5、X6、X7、X8或X9為氟。 X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 and X 9 are independently hydrogen or fluorine. In order to improve the dielectric anisotropy, preferred X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 or X 9 are fluorine.
Y1及Y2獨立地為氟、氯、至少1個氫經鹵素所取代的碳數1至12的烷基、至少1個氫經鹵素所取代的碳數1至12的烷氧基、或者至少1個氫經鹵素所取代的碳數2至12的烯氧基。為了降低下限溫度,較佳的Y1或Y2為氟。 Y 1 and Y 2 are independently fluorine, chlorine, an alkyl group having 1 to 12 carbons substituted by at least one hydrogen with halogen, an alkoxy group 1 to 12 carbon substituted with at least one hydrogen with halogen, or An alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is replaced with a halogen. In order to lower the lower limit temperature, preferred Y 1 or Y 2 is fluorine.
第五,示出較佳的成分化合物。較佳的化合物(1)為項2所述的化合物(1-1)至化合物(1-12)。該些化合物中,較佳為第一成分的至少1種為化合物(1-1)、化合物(1-2)、化合物(1-3)、化合物(1-4)、化合物(1-7)、化合物(1-8)、化合物(1-9)、化合物(1-10)、或者化合物(1-12)。較佳為第一成分的至少2種為化合物(1-3)及化合物(1-4)、化合物(1-3)及化合物(1-7)、化合物(1-4)及化合物(1-10)、或者化合物(1-10)及化合物(1-12)的組合。 Fifth, preferred component compounds are shown. Preferred compound (1) is the compound (1-1) to compound (1-12) according to item 2. Among these compounds, it is preferred that at least one of the first components is compound (1-1), compound (1-2), compound (1-3), compound (1-4), compound (1-7) , Compound (1-8), compound (1-9), compound (1-10), or compound (1-12). It is preferable that at least two kinds of the first component are compound (1-3) and compound (1-4), compound (1-3) and compound (1-7), compound (1-4) and compound (1- 10), or a combination of compound (1-10) and compound (1-12).
較佳的化合物(3)為項5所述的化合物(3-1)至化合物(3-12)。該些化合物中,較佳為第三成分的至少1種為化合物(3-2)、化合物(3-4)、化合物(3-5)、化合物(3-6)、化合物(3-9)、或者化合物(3-12)。較佳為第三成分的至少2種為化合物(3-2)及化合物(3-4)、化合物(3-2)及化合物(3-5)、或者化合物(3-2)及化合物(3-6)的組合。 Preferred compound (3) is the compound (3-1) to compound (3-12) according to item 5. Among these compounds, it is preferred that at least one of the third components is compound (3-2), compound (3-4), compound (3-5), compound (3-6), compound (3-9) Or compound (3-12). It is preferred that at least two of the third component be compound (3-2) and compound (3-4), compound (3-2) and compound (3-5), or compound (3-2) and compound (3 -6).
較佳的化合物(4)為項8所述的化合物(4-1)至化合物(4-24)。該些化合物中,較佳為第四成分的至少1種為化合物 (4-4)、化合物(4-9)、化合物(4-11)、化合物(4-12)、化合物(4-15)、化合物(4-16)、化合物(4-18)、或者化合物(4-19)。較佳為第四成分的至少2種為化合物(4-9)及化合物(4-12)、化合物(4-9)及化合物(4-18)、化合物(4-12)及化合物(4-15)、化合物(4-12)及化合物(4-18)、化合物(4-15)及化合物(4-18)、或者化合物(4-18)及化合物(4-19)的組合。 Preferred compound (4) is the compound (4-1) to compound (4-24) according to item 8. Of these compounds, it is preferred that at least one of the fourth components is a compound. (4-4), compound (4-9), compound (4-11), compound (4-12), compound (4-15), compound (4-16), compound (4-18), or compound (4-19). It is preferable that at least two kinds of the fourth component are compound (4-9) and compound (4-12), compound (4-9) and compound (4-18), compound (4-12) and compound (4- 15), compound (4-12) and compound (4-18), compound (4-15) and compound (4-18), or a combination of compound (4-18) and compound (4-19).
較佳的化合物(5)為項11所述的化合物(5-1)至化合物(5-19)。該些化合物中,較佳為第五成分的至少1種為化合物(5-1)、化合物(5-3)、化合物(5-4)、化合物(5-6)、化合物(5-8)、或者化合物(5-13)。較佳為第五成分的至少2種為化合物(5-1)及化合物(5-6)、化合物(5-1)及化合物(5-13)、化合物(5-3)及化合物(5-6)、化合物(5-3)及化合物(5-13)、化合物(5-4)及化合物(5-6)、或者化合物(5-4)及化合物(5-8)的組合。 Preferred compound (5) is the compound (5-1) to compound (5-19) according to item 11. Among these compounds, it is preferable that at least one of the fifth component is the compound (5-1), the compound (5-3), the compound (5-4), the compound (5-6), and the compound (5-8). Or compound (5-13). Preferably, at least two of the fifth component are the compound (5-1) and the compound (5-6), the compound (5-1) and the compound (5-13), the compound (5-3) and the compound (5- 6), compound (5-3) and compound (5-13), compound (5-4) and compound (5-6), or a combination of compound (5-4) and compound (5-8).
第六,對可添加於組成物中的添加物進行說明。此種添加物為光學活性化合物、抗氧化劑、紫外線吸收劑、色素、消泡劑、聚合性化合物、聚合起始劑、聚合抑制劑等。出於引起液晶的螺旋結構來賦予扭轉角(torsion angle)的目的,而將光學活性化合物添加於組成物中。此種化合物的例子為化合物(6-1)至化合物(6-5)。光學活性化合物的較佳比例為約5重量%以下。尤佳的比例為約0.01重量%至約2重量%的範圍。 Sixth, additives that can be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and the like. An optically active compound is added to the composition for the purpose of giving a torsion angle to the helical structure of the liquid crystal. Examples of such compounds are compound (6-1) to compound (6-5). A preferred ratio of the optically active compound is about 5 wt% or less. A particularly preferred ratio is in the range of about 0.01% by weight to about 2% by weight.
為了防止由大氣中的加熱所引起的比電阻下降,或者為了在長時間使用元件後,不僅在室溫下,而且在接近於上限溫度的溫度下亦維持大的電壓保持率,而將抗氧化劑添加於組成物中。抗氧化劑的較佳例是t為1至9的整數的化合物(7)等。 In order to prevent the decrease in specific resistance caused by heating in the atmosphere, or to maintain a large voltage holding ratio not only at room temperature, but also at a temperature close to the upper limit temperature, after using the element for a long time, antioxidants Added to the composition. Preferred examples of the antioxidant are a compound (7) and the like in which t is an integer of 1 to 9.
化合物(7)中,較佳的t為1、3、5、7或9。尤佳的t為7。t為7的化合物(7)由於揮發性小,故而對於在長時間使用元件後,不僅在室溫下,而且在接近於上限溫度的溫度下亦維持大的電壓保持率而言有效。為了獲得所述效果,抗氧化劑的較佳比例為約50ppm以上,為了不降低上限溫度,或者為了不提高下限溫度,抗氧化劑的較佳比例為約600ppm以下。尤佳的比例為約100ppm至約300ppm的範圍。 In compound (7), preferred t is 1, 3, 5, 7, or 9. A particularly preferred t is 7. The compound (7) with t of 7 is small in volatility, and is therefore effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after a long-term use of the device. In order to obtain the effect, a preferred ratio of the antioxidant is about 50 ppm or more, and in order not to lower the upper limit temperature, or not to raise the lower limit temperature, the preferred ratio of the antioxidant is about 600 ppm or less. A particularly preferred ratio is in the range of about 100 ppm to about 300 ppm.
紫外線吸收劑的較佳例為:二苯甲酮衍生物、苯甲酸酯衍生物、三唑衍生物等。另外,具有立體阻礙的胺之類的光穩定劑亦較佳。為了獲得所述效果,該些吸收劑或穩定劑的較佳比例為約50ppm以上,為了不降低上限溫度,或者為了不提高下限溫度,該些吸收劑或穩定劑的較佳比例為約10000ppm以下。尤佳的比例為約100ppm至約10000ppm的範圍。 Preferable examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, and triazole derivatives. In addition, a light stabilizer such as an amine having a steric hindrance is also preferable. In order to obtain the effect, the preferred ratio of these absorbers or stabilizers is about 50 ppm or more. In order not to lower the upper limit temperature, or to not raise the lower limit temperature, the preferred ratio of these absorbers or stabilizers is about 10,000 ppm or less . A particularly preferred ratio is in the range of about 100 ppm to about 10,000 ppm.
為了適合於賓主(guest host,GH)模式的元件,而將偶氮系色素、蒽醌系色素等之類的二色性色素(dichroic dye)添加於組成物中。色素的較佳比例為約0.01重量%至約10重量%的範圍。為了防止起泡,而將二甲基矽酮油、甲基苯基矽酮油等消泡劑添加於組成物中。為了獲得所述效果,消泡劑的較佳比例為 約1ppm以上,為了防止顯示不良,消泡劑的較佳比例為約1000ppm以下。尤佳的比例為約1ppm至約500ppm的範圍。 A dichroic dye such as an azo-based pigment, an anthraquinone-based pigment, or the like is added to the composition in order to be suitable for an element in a guest host (GH) mode. A preferred ratio of the pigment is in the range of about 0.01% by weight to about 10% by weight. To prevent foaming, antifoaming agents such as dimethyl silicone oil and methylphenyl silicone oil are added to the composition. In order to obtain the effect, a preferred ratio of the defoaming agent is About 1 ppm or more. In order to prevent poor display, the preferred ratio of the antifoaming agent is about 1000 ppm or less. A particularly preferred ratio is in the range of about 1 ppm to about 500 ppm.
為了適合於聚合物穩定配向(PSA)型的元件,而將聚合性化合物添加於組成物中。聚合性化合物的較佳例為丙烯酸酯、甲基丙烯酸酯、乙烯基化合物、乙烯氧基化合物、丙烯基醚、環氧化合物(氧雜環丙烷(oxirane)、氧雜環丁烷(oxetane))、乙烯基酮等具有可聚合的基團的化合物。尤佳的例子為丙烯酸酯或者甲基丙烯酸酯的衍生物。為了獲得所述效果,聚合性化合物的較佳比例為約0.05重量%以上,為了防止顯示不良,聚合性化合物的較佳比例為約10重量%以下。尤佳的比例為約0.1重量%至約2重量%的範圍。聚合性化合物藉由紫外線照射而聚合。亦可於光聚合起始劑等起始劑的存在下進行聚合。用以進行聚合的適當條件、起始劑的適當類型、以及適當的量已為本領域技術人員所知,並記載於文獻中。例如作為光起始劑的豔佳固(Irgacure)651(註冊商標;巴斯夫(BASF))、豔佳固(Irgacure)184(註冊商標;巴斯夫)、或者德牢固(Darocure)1173(註冊商標;巴斯夫)適合於自由基聚合。基於聚合性化合物的重量,光聚合起始劑的較佳比例為約0.1重量%至約5重量%的範圍。尤佳的比例為約1重量%至約3重量%的範圍。 A polymerizable compound is added to the composition in order to be suitable for a polymer stable alignment (PSA) type device. Preferred examples of the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, and epoxy compound (oxirane, oxetane). Compounds having a polymerizable group such as, vinyl ketone, and the like. Particularly preferred examples are derivatives of acrylates or methacrylates. In order to obtain the above effect, a preferable ratio of the polymerizable compound is about 0.05% by weight or more. In order to prevent display failure, a preferable ratio of the polymerizable compound is about 10% by weight or less. A particularly preferred ratio is in the range of about 0.1% by weight to about 2% by weight. The polymerizable compound is polymerized by irradiation with ultraviolet rays. Polymerization may be performed in the presence of an initiator such as a photopolymerization initiator. Suitable conditions for carrying out the polymerization, suitable types of initiators, and suitable amounts are known to those skilled in the art and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocure 1173 (registered trademark; BASF) as photoinitiators ) Suitable for free radical polymerization. The preferred ratio of the photopolymerization initiator is in the range of about 0.1% by weight to about 5% by weight based on the weight of the polymerizable compound. A particularly preferred ratio is in the range of about 1% by weight to about 3% by weight.
保管聚合性化合物時,為了防止聚合,亦可添加聚合抑制劑。聚合性化合物通常是以未去除聚合抑制劑的狀態添加於組成物中。聚合抑制劑的例子為對苯二酚(hydroquinone)、甲基對 苯二酚(methylhydroquinone)之類的對苯二酚衍生物、4-第三丁基鄰苯二酚(4-tert-butylcatechol)、4-甲氧基苯酚(4-methoxyphenol)、啡噻嗪(phenothiazine)等。 When storing a polymerizable compound, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, methyl para Hydroquinone derivatives such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, and phenothiazine ( phenothiazine), etc.
第七,對成分化合物的合成方法進行說明。該些化合物可利用已知的方法來合成。例示合成方法。化合物(1)是利用日本專利特開平10-81679號公報中記載的方法來合成。化合物(2)是利用日本專利特開昭59-176221號公報中記載的方法來合成。化合物(3-12)是利用日本專利特開平2-237949號公報中記載的方法來合成。化合物(4-2)及化合物(4-6)是利用日本專利特開平2-233626號公報中記載的方法來合成。化合物(5-1)及化合物(5-6)是利用日本專利特表平2-503441號公報中登載的方法來合成。抗氧化劑已有市售。式(7)的t為1的化合物可自西格瑪奧德里奇(Sigma-Aldrich Corporation)獲取。t為7的化合物(7)等是利用美國專利3660505號說明書中記載的方法來合成。 Seventh, a method for synthesizing the component compounds will be described. These compounds can be synthesized by known methods. Illustrative synthesis methods. Compound (1) is synthesized by a method described in Japanese Patent Laid-Open No. 10-81679. Compound (2) is synthesized by a method described in Japanese Patent Laid-Open No. 59-176221. Compound (3-12) is synthesized by the method described in Japanese Patent Laid-Open No. 2-237949. Compound (4-2) and compound (4-6) were synthesized by the method described in Japanese Patent Laid-Open No. 2-233626. The compound (5-1) and the compound (5-6) were synthesized by a method described in Japanese Patent Application Publication No. Hei 2-503441. Antioxidants are commercially available. The compound of formula (7) where t is 1 is available from Sigma-Aldrich Corporation. Compound (7) and the like where t is 7 are synthesized by a method described in US Pat. No. 3,660,505.
最後,對組成物的用途進行說明。本發明的組成物主要具有約-10℃以下的下限溫度、約70℃以上的上限溫度、以及約0.07至約0.20的範圍的光學各向異性。含有該組成物的元件具有大的電壓保持率。該組成物適合於AM元件。該組成物特別適合於透過型的AM元件。亦可藉由控制成分化合物的比例,或者藉由混合其他的液晶性化合物,來製備具有約0.08至約0.25的範圍的光學各向異性的組成物、進而具有約0.10至約0.30的範圍的光學各向異性的組成物。該組成物可用作具有向列相的組成物,且 可藉由添加光學活性化合物而用作光學活性組成物。 Finally, the use of the composition will be described. The composition of the present invention mainly has a lower limit temperature of about -10 ° C or lower, an upper limit temperature of about 70 ° C or higher, and optical anisotropy in a range of about 0.07 to about 0.20. The device containing this composition has a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for a transmissive AM device. It is also possible to prepare an optically anisotropic composition having a range of about 0.08 to about 0.25 by controlling the ratio of the component compounds or mixing other liquid crystal compounds, and further have an optical range of about 0.10 to about 0.30 Anisotropic composition. The composition can be used as a composition having a nematic phase, and It can be used as an optically active composition by adding an optically active compound.
該組成物可用於AM元件。進而亦可用於PM元件。該組成物可用於具有PC、TN、STN、ECB、OCB、IPS、FFS、VA、FPA等模式的AM元件及PM元件。特佳為用於具有TN模式、OCB模式、IPS模式或者FFS模式的AM元件。於具有IPS模式或者FFS模式的AM元件中,當未施加電壓時,相對於玻璃基板,液晶分子的排列可為平行,或者亦可為垂直。該些元件可為反射型、透過型或者半透過型。較佳為用於透過型元件。亦可用於非晶矽-TFT元件或者多晶矽-TFT元件。亦可用於將該組成物進行微膠囊化而製作的向列曲線排列相(nematic curvilinear aligned phase,NCAP)型元件、或使組成物中形成有三維網狀高分子的聚合物分散(polymer dispersed,PD)型元件。 This composition can be used for an AM device. It can also be used for PM devices. This composition can be used for AM devices and PM devices with PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA and other modes. Particularly preferred is for AM elements having a TN mode, an OCB mode, an IPS mode, or an FFS mode. In an AM device having an IPS mode or an FFS mode, when no voltage is applied, the arrangement of the liquid crystal molecules with respect to the glass substrate may be parallel or vertical. These devices can be reflective, transmissive, or transflective. It is preferably used for a transmissive element. It can also be used for amorphous silicon-TFT elements or polycrystalline silicon-TFT elements. It can also be used for nematic curvilinear aligned phase (NCAP) elements made by microencapsulating this composition, or polymer dispersed (polymer dispersed, three-dimensional network polymers) formed in the composition. PD) type element.
[實施例] [Example]
藉由實施例來對本發明進一步進行詳細說明。本發明不受該些實施例的限制。所合成的化合物是藉由核磁共振(nuclear magnetic resonance,NMR)分析等方法來鑑定。化合物以及組成物的特性是利用下述記載的方法來測定。 The present invention will be further described in detail through examples. The invention is not limited by these examples. The synthesized compounds were identified by methods such as nuclear magnetic resonance (NMR) analysis. The properties of the compounds and compositions were measured by the methods described below.
NMR分析:測定時使用布魯克拜厄斯賓(Bruker BioSpin)公司製造的DRX-500。1H-NMR的測定中,使試樣溶解於CDCl3等氘化溶劑中,於室溫下以500MHz、累計次數為16次的條件進行測定。使用四甲基矽烷作為內部標準。19F-NMR的測定中,使用CFCl3作為內部標準,以累計次數24次來進行。核磁 共振光譜的說明中,s是指單峰(singlet),d是指雙重峰(doublet),t是指三重峰(triplet),q是指四重峰(quartet),quin是指五重峰(quintet),sex是指六重峰(sextet),m是指多重峰(multiplet),br是指寬峰(broad)。 NMR analysis: For measurement, DRX-500 manufactured by Bruker BioSpin was used. In the measurement of 1 H-NMR, the sample was dissolved in a deuterated solvent such as CDCl 3 and the measurement was performed at room temperature under the conditions of 500 MHz and a cumulative number of 16 times. Tetramethylsilane was used as the internal standard. In the 19 F-NMR measurement, CFCl 3 was used as an internal standard, and the total number of measurements was performed 24 times. In the description of the nuclear magnetic resonance spectrum, s refers to singlet, d refers to doublet, t refers to triplet, q refers to quartet, and quin refers to quintet. (quintet), sex refers to a sextet, (sextet), m refers to a multiplet, and br refers to a broad peak.
氣相層析分析:測定是使用島津製作所製造的GC-14B型氣相層析儀。載體氣體為氦氣(2mL/min)。將試樣氣化室設定為280℃,將檢測器(火焰離子化檢測器(flame ionization detector,FID))設定為300℃。進行成分化合物的分離時使用安捷倫科技有限公司(Agilent Technologies Inc.)製造的毛細管柱DB-1(長度30m、內徑0.32mm、膜厚0.25μm;固定液相為二甲基聚矽氧烷;無極性)。該管柱於200℃下保持2分鐘後,以5℃/min的比例升溫至280℃。將試樣製備成丙酮溶液(0.1重量%)後,將其1μL注入至試樣氣化室中。記錄計為島津製作所製造的C-R5A型層析儀組件(Chromatopac)、或者其同等品。所得的氣相層析圖表示與成分化合物相對應的峰值的保持時間以及峰值的面積。 Gas chromatography analysis: The measurement was performed using a GC-14B gas chromatograph manufactured by Shimadzu Corporation. The carrier gas was helium (2 mL / min). The sample gasification chamber was set to 280 ° C, and the detector (flame ionization detector (FID)) was set to 300 ° C. For separation of component compounds, a capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. was used; the fixed liquid phase was dimethylpolysiloxane; Non-polar). After the column was held at 200 ° C for 2 minutes, the temperature was raised to 280 ° C at a rate of 5 ° C / min. After preparing a sample as an acetone solution (0.1% by weight), 1 μL of the sample was injected into the sample gasification chamber. The recorder is a C-R5A Chromatopac manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram shows the retention time of the peak corresponding to the component compounds and the area of the peak.
用以稀釋試樣的溶劑可使用氯仿、己烷等。為了將成分化合物分離,可使用如下的毛細管柱。安捷倫科技有限公司製造的HP-1(長度30m、內徑0.32mm、膜厚0.25μm)、瑞斯泰克公司(Restek Corporation)製造的Rtx-1(長度30m、內徑0.32mm、膜厚0.25μm)、澳大利亞SGE國際公司(SGE International Pty.Ltd)製造的BP-1(長度30m、內徑0.32mm、膜厚0.25μm)。 出於防止化合物峰值的重疊的目的,可使用島津製作所製造的毛細管柱CBP1-M50-025(長度50m、內徑0.25mm、膜厚0.25μm)。 As a solvent for diluting the sample, chloroform, hexane, or the like can be used. To separate the component compounds, the following capillary columns can be used. HP-1 manufactured by Agilent Technologies Co., Ltd. (length 30m, inner diameter 0.32mm, film thickness 0.25μm), Rtx-1 manufactured by Restek Corporation (length 30m, inner diameter 0.32mm, film thickness 0.25μm ), BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by SGE International Pty. Ltd. of Australia. To prevent the compound peaks from overlapping, a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, and film thickness 0.25 μm) manufactured by Shimadzu Corporation can be used.
組成物中所含有的液晶性化合物的比例可利用如下所述的方法來算出。利用氣相層析儀(FID)來對液晶性化合物的混合物進行檢測。氣相層析圖中的峰值的面積比相當於液晶性化合物的比例(重量比)。使用上文記載的毛細管柱時,可將各種液晶性化合物的修正係數視為1。因此,液晶性化合物的比例(重量%)可根據峰值的面積比來算出。 The ratio of the liquid crystal compound contained in the composition can be calculated by the method described below. A gas chromatograph (FID) was used to detect a mixture of liquid crystal compounds. The area ratio of the peaks in the gas chromatogram corresponds to the ratio (weight ratio) of the liquid crystal compound. When the capillary column described above is used, the correction coefficient of various liquid crystal compounds can be regarded as one. Therefore, the ratio (% by weight) of the liquid crystalline compound can be calculated from the peak area ratio.
測定試樣:測定組成物的特性時,將組成物直接用作試樣。測定化合物的特性時,藉由將該化合物(15重量%)混合於母液晶(85重量%)中來製備測定用試樣。根據藉由測定而獲得的值,利用外推法來算出化合物的特性值。(外推值)={(試樣的測定值)-0.85×(母液晶的測定值)}/0.15。當於該比例下,層列相(或者結晶)於25℃下析出時,將化合物與母液晶的比例以10重量%:90重量%、5重量%:95重量%、1重量%:99重量%的順序變更。利用該外推法來求出與化合物相關的上限溫度、光學各向異性、黏度、以及介電各向異性的值。 Measurement sample: When measuring the characteristics of a composition, the composition is directly used as a sample. When measuring the characteristics of a compound, a sample for measurement was prepared by mixing the compound (15% by weight) with a mother liquid crystal (85% by weight). From the values obtained by the measurement, the characteristic values of the compounds were calculated by extrapolation. (Extrapolated value) = {(measured value of sample) -0.85 × (measured value of mother liquid crystal)} / 0.15. When the smectic phase (or crystal) is precipitated at 25 ° C at this ratio, the ratio of the compound to the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, and 1% by weight: 99% % Order change. This extrapolation method was used to determine the values of the compound-dependent upper temperature, optical anisotropy, viscosity, and dielectric anisotropy.
使用下述母液晶。成分化合物的比例是以重量%表示。 The following mother liquid crystals were used. The proportion of the component compounds is expressed in% by weight.
測定方法:利用下述方法來進行特性的測定。該些方法大多是社團法人電子資訊技術產業協會(Japan Electronics and Information Technology Industries Association;以下稱為JEITA)所審議製定的JEITA標準(JEITA.ED-2521B)中記載的方法、或者將其加以修飾而成的方法。用於測定的TN元件上未安裝薄膜電晶體(thin film transistor,TFT)。 Measurement method: The characteristics were measured by the following method. These methods are mostly methods described in the JEITA standard (JEITA.ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA) or modified and modified.成 的 方法。 into the method. A thin film transistor (TFT) was not mounted on the TN device used for the measurement.
(1)向列相的上限溫度(NI;℃):於具備偏光顯微鏡的熔點測定裝置的加熱板上放置試樣,以1℃/min的速度進行加熱。測定試樣的一部分自向列相變化為各向同性液體時的溫度。 (1) Upper limit temperature (NI; ° C) of the nematic phase: A sample is placed on a hot plate of a melting point measuring device equipped with a polarizing microscope, and heated at a rate of 1 ° C / min. The temperature at which a part of the sample changed from a nematic phase to an isotropic liquid was measured.
(2)向列相的下限溫度(TC;℃):將具有向列相的試樣放入玻璃瓶中,於0℃、-10℃、-20℃、-30℃及-40℃的冷凍器中保管10天後,觀察液晶相。例如,當試樣於-20℃下為向列相的狀態,而於-30℃下變化為結晶或者層列相時,將TC記載為<-20℃。 (2) Lower limit temperature of nematic phase (T C ; ℃): Put the sample with nematic phase into the glass bottle at 0 ℃, -10 ℃, -20 ℃, -30 ℃ and -40 ℃. After storing in a freezer for 10 days, the liquid crystal phase was observed. For example, when the sample is in the state of a nematic phase at -20 ° C and changes to a crystal or a smectic phase at -30 ° C, T C is described as <-20 ° C.
(3)黏度(體積黏度;η;於20℃下測定;mPa.s):測定時使用東京計器股份有限公司製造的E型旋轉黏度計。 (3) Viscosity (volume viscosity; η; measured at 20 ° C; mPa.s): For measurement, an E-type rotary viscometer manufactured by Tokyo Keiki Co., Ltd. was used.
(4)黏度(旋轉黏度;γ1;於25℃下測定;mPa.s):依據M.今井(M.Imai)等人的「分子晶體與液晶(Molecular Crystals and Liquid Crystals)」第259期第37頁(1995)中記載的方法來進行測定。於扭轉角為0°且2塊玻璃基板的間隔(單元間隙)為5μm的TN元件中放入試樣。對該元件於16V至19.5V的範圍內,以0.5V為單位階段性地施加電壓。不施加電壓0.2秒後,以僅施加1個矩形波(矩形脈衝;0.2秒)與不施加電壓(2秒)的條件反覆施加。測定藉由該施加而產生的暫態電流(transient current)的峰值電流(peak current)及峰值時間(peak time)。由該些測定值與M.今井等人的論文中的第40頁記載的計算式(8)來獲得旋轉黏度的值。該計算所需要的介電各向異性的值是使用該測定了旋轉黏度的元件,利用下文記載的方法而求出。 (4) Viscosity (rotational viscosity; γ1; measured at 25 ° C; mPa.s): According to "Molecular Crystals and Liquid Crystals" by M. Imai et al. No. 259th The measurement is performed by the method described in page 37 (1995). A sample was placed in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 μm. A voltage was applied to the element in a range of 16V to 19.5V in steps of 0.5V. 0.2 seconds after no voltage was applied, it was repeatedly applied under the conditions of applying only one rectangular wave (rectangular pulse; 0.2 second) and no voltage (2 seconds). The peak current and peak time of a transient current generated by the application were measured. From these measured values and the calculation formula (8) described on page 40 in the paper by M. Imai et al., The value of the rotational viscosity was obtained. The value of the dielectric anisotropy required for the calculation is obtained by using the device whose rotational viscosity is measured by a method described below.
(5)光學各向異性(折射率各向異性;△n;於25℃下測定):使用波長為589nm的光,利用在接目鏡上安裝有偏光板的阿貝折射計來進行測定。將主稜鏡的表面向一個方向摩擦後,將試樣滴加於主稜鏡上。折射率n ∥是在偏光的方向與摩擦的方向平行時進行測定。折射率n ⊥是在偏光的方向與摩擦的方向垂直時進行測定。光學各向異性的值是根據△n=n ∥-n ⊥的式子來計算。 (5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C): Measurement was performed using an Abbe refractometer with a polarizing plate attached to an eyepiece using light having a wavelength of 589 nm. After rubbing the surface of the main shaft in one direction, the sample was dropped on the main shaft. The refractive index n 测定 is measured when the direction of polarized light is parallel to the direction of rubbing. The refractive index n 测定 is measured when the direction of polarized light is perpendicular to the direction of rubbing. The value of optical anisotropy is calculated according to the formula of Δn = n ∥-n ⊥.
(6)介電各向異性(△ε;於25℃下測定):於2塊玻璃基板的間隔(單元間隙)為9μm且扭轉角為80度的TN元件中 放入試樣。對該元件施加正弦波(10V、1kHz),2秒後測定液晶分子的長軸方向的介電常數(ε ∥)。對該元件施加正弦波(0.5V、1kHz),2秒後測定液晶分子的短軸方向的介電常數(ε ⊥)。根據△ε=ε ∥-ε ⊥的式子來計算出介電各向異性的值。 (6) Dielectric anisotropy (Δε; measured at 25 ° C): In a TN device in which the distance (cell gap) between two glass substrates is 9 μm and the twist angle is 80 degrees Place the sample. A sine wave (10 V, 1 kHz) was applied to the device, and the dielectric constant (ε ∥) of the long axis direction of the liquid crystal molecules was measured 2 seconds later. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε ⊥) of the minor axis direction of the liquid crystal molecules was measured after 2 seconds. The value of dielectric anisotropy was calculated according to the formula of Δε = ε ∥-ε ⊥.
(7)臨限電壓(Vth;於25℃下測定;V):測定時使用大塚電子股份有限公司製造的LCD5100型亮度計。光源為鹵素燈。於2塊玻璃基板的間隔(單元間隙)為0.45/△n(μm)且扭轉角為80度的正常顯白模式(normally white mode)的TN元件中放入試樣。對該元件施加的電壓(32Hz、矩形波)是以0.02V為單位,自0V階段性地增加至10V。此時,自垂直方向對元件照射光,測定透過元件的光量。製成當該光量達到最大時透過率為100%,且當該光量為最小時透過率為0%的電壓-透過率曲線。臨限電壓是由透過率達到90%時的電壓來表示。 (7) Threshold voltage (Vth; measured at 25 ° C; V): The LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. A sample was placed in a normally white mode TN device in which the distance (cell gap) between two glass substrates was 0.45 / Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, rectangular wave) applied to the device was increased in steps from 0 V to 10 V in units of 0.02 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve having a transmittance of 100% when the amount of light reaches the maximum and a transmittance of 0% when the amount of light is the smallest is made. The threshold voltage is expressed by the voltage when the transmittance reaches 90%.
(8)電壓保持率(VHR-1;於25℃下測定;%):測定中使用的TN元件具有聚醯亞胺配向膜,而且2塊玻璃基板的間隔(單元間隙)為5μm。加入試樣後,利用以紫外線進行硬化的黏接劑將該元件密封。對該TN元件施加脈衝電壓(5V、60微秒)來充電。利用高速電壓計在16.7毫秒之間測定所衰減的電壓,求出單位週期中的電壓曲線與橫軸之間的面積A。面積B為未衰減時的面積。電壓保持率是由面積A相對於面積B的百分率來表示。 (8) Voltage holding ratio (VHR-1; measured at 25 ° C;%): The TN device used in the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. After the sample is added, the element is sealed with an adhesive that is hardened with ultraviolet rays. A pulse voltage (5 V, 60 microseconds) was applied to the TN element to charge it. The decaying voltage was measured between 16.7 milliseconds using a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was obtained. The area B is the area without attenuation. The voltage holding ratio is expressed as a percentage of the area A to the area B.
(9)電壓保持率(VHR-2;於80℃下測定;%):除了代替25℃而於80℃下進行測定以外,以與所述相同的程序來測定 電壓保持率。將所得的值以VHR-2來表示。 (9) Voltage holding ratio (VHR-2; measured at 80 ° C;%): Measured by the same procedure as described above, except that the measurement is performed at 80 ° C instead of 25 ° C. Voltage holding rate. The obtained value is represented by VHR-2.
(10)電壓保持率(VHR-3;於25℃下測定;%):照射紫外線後,測定電壓保持率,來評價對紫外線的穩定性。測定中使用的TN元件具有聚醯亞胺配向膜,而且單元間隙為5μm。於該元件中注入試樣,照射光20分鐘。光源為超高壓水銀燈USH-500D(牛尾(Ushio)電機製造),元件與光源的間隔為20cm。VHR-3的測定中,於16.7毫秒之間測定所衰減的電壓。具有大的VHR-3的組成物對紫外線具有大的穩定性。VHR-3較佳為90%以上,更佳為95%以上。 (10) Voltage holding ratio (VHR-3; measured at 25 ° C;%): After irradiation with ultraviolet rays, the voltage holding ratio was measured to evaluate the stability to ultraviolet rays. The TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 μm. A sample was injected into the device, and the device was irradiated with light for 20 minutes. The light source is an ultra-high pressure mercury lamp USH-500D (made by Ushio Motor), and the distance between the element and the light source is 20 cm. In the measurement of VHR-3, the attenuated voltage was measured between 16.7 milliseconds. A composition having a large VHR-3 has a large stability to ultraviolet rays. VHR-3 is preferably 90% or more, and more preferably 95% or more.
(11)電壓保持率(VHR-4;於25℃下測定;%):將注入有試樣的TN元件於80℃的恆溫槽內加熱500小時後,測定電壓保持率,來評價對熱的穩定性。VHR-4的測定中,於16.7毫秒之間測定所衰減的電壓。具有大的VHR-4的組成物對熱具有大的穩定性。 (11) Voltage holding ratio (VHR-4; measured at 25 ° C;%): After heating the TN device filled with the sample in a constant temperature bath at 80 ° C for 500 hours, the voltage holding ratio was measured to evaluate the thermal resistance stability. In the measurement of VHR-4, the attenuated voltage was measured between 16.7 milliseconds. A composition having a large VHR-4 has a large stability to heat.
(12)響應時間(τ;於25℃下測定;ms):測定時使用大塚電子股份有限公司製造的LCD5100型亮度計。光源為鹵素燈。低通濾波器(Low-pass filter)設定為5kHz。於2塊玻璃基板的間隔(單元間隙)為5.0μm且扭轉角為80度的正常顯白模式(normally white mode)的TN元件中放入試樣。對該元件施加矩形波(60Hz、5V、0.5秒)。此時,自垂直方向對元件照射光,測定透過元件的光量。該光量達到最大時視為透過率100%,該光量為最小時視為透過率0%。上升時間(τr:rise time;毫秒)是 透過率自90%變化為10%所需要的時間。下降時間(τf:fall time;毫秒)是透過率自10%變化為90%所需要的時間。響應時間是由以所述方式求出的上升時間與下降時間之和來表示。 (12) Response time (τ; measured at 25 ° C; ms): The LCD5100 brightness meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. The low-pass filter is set to 5 kHz. A sample was placed in a normally white mode TN device in which the distance (cell gap) between two glass substrates was 5.0 μm and the twist angle was 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to the device. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. When the light amount reaches the maximum, the transmittance is regarded as 100%, and when the light amount is the minimum, the transmittance is regarded as 0%. Rise time (τr: rise time; milliseconds) is Time required for the transmittance to change from 90% to 10%. Fall time (τf: fall time; milliseconds) is the time required for the transmittance to change from 10% to 90%. The response time is represented by the sum of the rise time and the fall time obtained in the manner described above.
(13)彈性常數(K;於25℃下測定;pN):測定時使用橫河惠普(Yokogawa-Hewlett-Packard)股份有限公司製造的HP4284A型LCR計。於2塊玻璃基板的間隔(單元間隙)為20μm的水平配向元件中放入試樣。對該元件施加0伏特至20伏特電荷,測定靜電電容以及施加電壓。使用「液晶裝置手冊」(日刊工業新聞社)第75頁的式(2.98)、式(2.101),將所測定的靜電電容(C)與施加電壓(V)的值進行擬合,由式(2.99)獲得K11及K33的值。繼而於所述「液晶裝置手冊」第171頁的式(3.18)中,使用剛才求出的K11及K33的值來算出K22。彈性常數是由以所述方式求出的K11、K22及K33的平均值來表示。 (13) Elastic constant (K; measured at 25 ° C; pN): The HP4284A type LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. was used for the measurement. A sample was placed in a horizontal alignment element having a distance (cell gap) between two glass substrates of 20 μm. A charge of 0 volts to 20 volts was applied to the device, and the capacitance and the applied voltage were measured. Using equations (2.98) and (2.101) on page 75 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), the measured capacitance (C) and the value of the applied voltage (V) are fitted, and the equation ( 2.99) Obtain the values of K11 and K33. Then, in formula (3.18) on page 171 of the "Liquid Crystal Device Handbook", K22 was calculated using the values of K11 and K33 just obtained. The elastic constant is represented by the average value of K11, K22, and K33 calculated | required as mentioned above.
(14)比電阻(ρ;於25℃下測定;Ωcm):於具備電極的容器中注入試樣1.0mL。對該容器施加直流電壓(10V),測定10秒後的直流電流。由下式來算出比電阻。(比電阻)={(電壓)×(容器的電容)}/{(直流電流)×(真空的介電常數)}。 (14) Specific resistance (ρ; measured at 25 ° C; Ωcm): 1.0 mL of a sample was poured into a container provided with an electrode. A DC voltage (10 V) was applied to the container, and a DC current after 10 seconds was measured. The specific resistance is calculated from the following formula. (Specific resistance) = {(voltage) × (capacitance of the container)} / {(DC current) × (dielectric constant of vacuum)}.
(15)螺旋節距(P;於室溫下測定;μm):螺旋節距是利用楔法來測定。參照「液晶便覽」第196頁(2000年發行,丸善)。將試樣注入至楔形單元中,於室溫下靜置2小時後,利用偏光顯微鏡(尼康(Nikon)(股),商品名MM40/60系列)來觀察向錯線(disclination line)的間隔(d2-d1)。螺旋節距(P)是根 據將楔單元的角度表示為θ的下述式來算出。P=2×(d2-d1)×tanθ。 (15) Spiral pitch (P; measured at room temperature; μm): The spiral pitch is measured by the wedge method. Refer to "LCD Fact Sheet" on page 196 (issued in 2000, Maruzen). The sample was injected into the wedge-shaped unit and left at room temperature for 2 hours, and then the interval of the disclination line was observed using a polarizing microscope (Nikon (stock), trade name MM40 / 60 series) ( d2-d1). Helix pitch (P) is the root The angle of the wedge element is calculated by the following expression, which is θ. P = 2 × (d2-d1) × tanθ.
(16)短軸方向的介電常數(ε ⊥;於25℃下測定):於2塊玻璃基板的間隔(單元間隙)為9μm且扭轉角為80度的TN元件中放入試樣。對該元件施加正弦波(0.5V、1kHz),2秒後測定液晶分子的短軸方向的介電常數(ε ⊥)。 (16) Dielectric constant in the minor axis direction (ε ⊥; measured at 25 ° C.): A sample was placed in a TN device in which the distance (cell gap) between two glass substrates was 9 μm and the twist angle was 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε ⊥) of the minor axis direction of the liquid crystal molecules was measured after 2 seconds.
實施例中的化合物是基於下述表3的定義,利用記號來表示。表3中,與1,4-伸環己基有關的立體構型為反式構型。位於記號後的括弧內的編號與化合物的編號相對應。(-)的記號是指其他的液晶性化合物。液晶性化合物的比例(百分率)是基於液晶組成物的重量的重量百分率(重量%)。最後,歸納組成物的特性值。 The compounds in the examples are represented by symbols based on the definitions in Table 3 below. In Table 3, the stereo configuration related to 1,4-cyclohexyl is a trans configuration. The number in parentheses after the mark corresponds to the number of the compound. The symbol (-) means another liquid crystal compound. The ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the characteristic values of the composition are summarized.
[比較例1] [Comparative Example 1]
自日本專利特開平10-81679號公報中揭示的組成物中選擇實 施例33。根據為該組成物含有化合物(1)、化合物(3-1)、化合物(3-4)、化合物(4)及化合物(2)的類似化合物,且不含有氰基化合物。該組成物的成分及特性如下所述。 It is selected from the composition disclosed in Japanese Patent Laid-Open No. 10-81679 Example 33. It is believed that this composition contains compounds (1), (3-1), (3-4), (4) and similar compounds of compound (2), and does not contain a cyano compound. The components and characteristics of the composition are as follows.
NI=86.5℃;△n=0.099;△ε=5.3;Vth=2.18V;η=23.5mPa.s. NI = 86.5 ℃; △ n = 0.099; △ ε = 5.3; Vth = 2.18V; η = 23.5mPa. s.
[實施例1] [Example 1]
將比較例1的組成物中所含有的化合物(2)的類似化合物替換為化合物(2),製成本申請案的組成物。該組成物的成分及特性如下所述。 A compound similar to the compound (2) contained in the composition of Comparative Example 1 was replaced with the compound (2) to prepare a composition of the present application. The components and characteristics of the composition are as follows.
NI=85.7℃;△n=0.099;△ε=5.2;Vth=2.17V;η=22.4mPa.s. NI = 85.7 ℃; △ n = 0.099; △ ε = 5.2; Vth = 2.17V; η = 22.4mPa. s.
[實施例2] [Example 2]
NI=86.7℃;Tc<-20℃;△n=0.121;△ε=2.7;Vth=2.76V;η=13.5mPa.s;γ1=75.8mPa.s;ε ⊥/△ε=1.33. NI = 86.7 ℃; Tc <-20 ℃; Δn = 0.121; Δε = 2.7; Vth = 2.76V; η = 13.5mPa. s; γ1 = 75.8mPa. s; ε ⊥ / △ ε = 1.33.
[實施例3] [Example 3]
NI=86.5℃;Tc<-20℃;△n=0.094;△ε=8.0;Vth=1.53V;η=16.5mPa.s;γ1=92.4mPa.s. NI = 86.5 ℃; Tc <-20 ℃; △ n = 0.094; △ ε = 8.0; Vth = 1.53V; η = 16.5mPa. s; γ1 = 92.4mPa. s.
[實施例4] [Example 4]
NI=81.2℃;Tc<-20℃;△n=0.114;△ε=2.9;Vth=2.72V;η=13.3mPa.s;γ1=75.1mPa.s;ε ⊥/△ε=1.20. NI = 81.2 ℃; Tc <-20 ℃; △ n = 0.114; △ ε = 2.9; Vth = 2.72V; η = 13.3mPa. s; γ1 = 75.1mPa. s; ε ⊥ / △ ε = 1.20.
[實施例5] [Example 5]
NI=101.9℃;Tc<-20℃;△n=0.116;△ε=5.4;Vth=1.83V;η=22.6mPa.s. NI = 101.9 ℃; Tc <-20 ℃; Δn = 0.116; Δε = 5.4; Vth = 1.83V; η = 22.6mPa. s.
[實施例6] [Example 6]
NI=102.9℃;Tc<-20℃;△n=0.107;△ε=6.1;Vth=1.78V;η=22.7mPa.s. NI = 102.9 ℃; Tc <-20 ℃; Δn = 0.107; Δε = 6.1; Vth = 1.78V; η = 22.7mPa. s.
[實施例7] [Example 7]
NI=93.5℃;Tc<-20℃;△n=0.108;△ε=5.4;Vth=1.88V;η=14.8 mPa.s;γ1=82.9mPa.s;ε ⊥/△ε=0.68. NI = 93.5 ℃; Tc <-20 ℃; △ n = 0.108; △ ε = 5.4; Vth = 1.88V; η = 14.8 mPa. s; γ1 = 82.9mPa. s; ε ⊥ / △ ε = 0.68.
[實施例8] [Example 8]
NI=82.3℃;Tc<-20℃;△n=0.099;△ε=4.3;Vth=1.96V;η=12.3 mPa.s;γ1=68.9mPa.s. NI = 82.3 ℃; Tc <-20 ℃; △ n = 0.099; △ ε = 4.3; Vth = 1.96V; η = 12.3 mPa. s; γ1 = 68.9mPa. s.
[實施例9] [Example 9]
NI=92.5℃;Tc<-20℃;△n=0.127;△ε=5.7;Vth=1.83V;η=15.8mPa.s;γ1=88.5mPa.s;ε ⊥/△ε=0.63. NI = 92.5 ℃; Tc <-20 ℃; △ n = 0.127; △ ε = 5.7; Vth = 1.83V; η = 15.8mPa. s; γ1 = 88.5mPa. s; ε ⊥ / △ ε = 0.63.
[實施例10] [Example 10]
NI=92.3℃;Tc<-20℃;△n=0.115;△ε=4.0;Vth=2.28V;η=16.4mPa.s;γ1=91.8mPa.s. NI = 92.3 ℃; Tc <-20 ℃; △ n = 0.115; △ ε = 4.0; Vth = 2.28V; η = 16.4mPa. s; γ1 = 91.8mPa. s.
[實施例11] [Example 11]
NI=97.6℃;Tc<-20℃;△n=0.089;△ε=2.9;Vth=2.73V;η=19.2mPa.s. NI = 97.6 ℃; Tc <-20 ℃; △ n = 0.089; △ ε = 2.9; Vth = 2.73V; η = 19.2mPa. s.
[實施例12] [Example 12]
NI=88.6℃;Tc<-20℃;△n=0.095;△ε=4.4;Vth=1.95V;η=11.4mPa.s;γ1=63.8mPa.s. NI = 88.6 ℃; Tc <-20 ℃; △ n = 0.095; △ ε = 4.4; Vth = 1.95V; η = 11.4mPa. s; γ1 = 63.8mPa. s.
[實施例13] [Example 13]
NI=85.1℃;Tc<-20℃;△n=0.099;△ε=6.7;Vth=1.70V;η=16.5mPa.s. NI = 85.1 ℃; Tc <-20 ℃; △ n = 0.099; △ ε = 6.7; Vth = 1.70V; η = 16.5mPa. s.
[實施例14] [Example 14]
NI=78.9℃;Tc<-20℃;△n=0.119;△ε=6.9;Vth=1.68V;η=17.5mPa.s. NI = 78.9 ℃; Tc <-20 ℃; △ n = 0.119; △ ε = 6.9; Vth = 1.68V; η = 17.5mPa. s.
[實施例15] [Example 15]
NI=85.6℃;Tc<-20℃;△n=0.121;△ε=5.7;Vth=1.85V;η=13.2mPa.s;γ1=73.9mPa.s;ε⊥/△ε=0.65. NI = 85.6 ℃; Tc <-20 ℃; △ n = 0.121; △ ε = 5.7; Vth = 1.85V; η = 13.2mPa. s; γ1 = 73.9mPa. s; ε⊥ / △ ε = 0.65.
比較例1的組成物的黏度(η)為23.5。另一方面,實施例1的組成物的黏度為22.4。如此,與比較例的組成物相比,含有化合物(2)實施例的組成物具有小的黏度。因此,結論為本發明的液晶組成物具有優異的特性。 The viscosity (η) of the composition of Comparative Example 1 was 23.5. On the other hand, the viscosity of the composition of Example 1 was 22.4. As such, the composition containing the compound (2) example has a smaller viscosity than the composition of the comparative example. Therefore, it was concluded that the liquid crystal composition of the present invention has excellent characteristics.
本發明的液晶組成物於高的上限溫度、低的下限溫度、小的黏度、適當的光學各向異性、大的介電各向異性、大的比電阻、對紫外線的高穩定性、對熱的高穩定性、大的彈性常數等特性中,滿足至少1種特性,或者關於至少2種特性而具有適當的平衡。含有該組成物的液晶顯示元件由於具有短的響應時間、大的電壓保持率、大的對比度比、長的壽命等,故而可用於液晶投影機、液晶電視等。 The liquid crystal composition of the present invention has a high upper limit temperature, a low lower limit temperature, a small viscosity, an appropriate optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability to ultraviolet rays, and a high resistance to heat. Among the characteristics such as high stability, large elastic constant, etc., at least one characteristic is satisfied, or at least two characteristics are appropriately balanced. The liquid crystal display element containing the composition has a short response time, a large voltage holding ratio, a large contrast ratio, a long life, and the like, and thus can be used for a liquid crystal projector, a liquid crystal television, and the like.
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JPWO2015151607A1 (en) * | 2014-03-31 | 2017-04-13 | Jnc株式会社 | Liquid crystal display element and liquid crystal composition |
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KR102312261B1 (en) * | 2015-04-30 | 2021-10-13 | 삼성디스플레이 주식회사 | Liquid crystal composition and liquid crystal display including the same |
KR20180016996A (en) * | 2015-06-12 | 2018-02-20 | 디아이씨 가부시끼가이샤 | Composition and liquid crystal display element using same |
CN105038816B (en) * | 2015-07-13 | 2017-09-29 | 石家庄诚志永华显示材料有限公司 | Liquid-crystal composition |
CN105542794B (en) * | 2016-02-01 | 2017-12-01 | 北京华科嘉泰科技有限公司 | A kind of liquid-crystal composition and its application |
WO2017183468A1 (en) * | 2016-04-20 | 2017-10-26 | Dic株式会社 | Composition and liquid crystal display element using same |
KR20180029142A (en) * | 2016-09-09 | 2018-03-20 | 삼성디스플레이 주식회사 | Liquid crystal composition and liquid crystal display including the same |
KR102377501B1 (en) * | 2016-10-27 | 2022-03-21 | 제이엔씨 주식회사 | Liquid crystal composition for dimming and liquid crystal dimming element |
CN108219802B (en) * | 2016-12-14 | 2021-11-02 | 江苏和成显示科技有限公司 | Liquid crystal composition and application thereof |
CN108165279B (en) * | 2018-03-08 | 2020-07-07 | 京东方科技集团股份有限公司 | Liquid crystal composition, preparation method, display panel and display device |
CN111117650B (en) * | 2018-10-30 | 2022-01-18 | 江苏和成显示科技有限公司 | Liquid crystal composition and display device thereof |
CN111117651B (en) * | 2018-10-30 | 2022-02-22 | 江苏和成显示科技有限公司 | Liquid crystal composition and display device thereof |
CN111117648B (en) * | 2018-10-30 | 2022-08-23 | 江苏和成显示科技有限公司 | Liquid crystal composition and display device thereof |
CN111117647B (en) * | 2018-10-30 | 2022-02-22 | 江苏和成显示科技有限公司 | Liquid crystal composition and display device thereof |
CN111117654B (en) * | 2018-10-30 | 2022-02-22 | 江苏和成显示科技有限公司 | Liquid crystal composition and display device thereof |
CN111117655B (en) * | 2018-10-30 | 2022-01-18 | 江苏和成显示科技有限公司 | Liquid crystal composition and display device thereof |
CN111117649B (en) * | 2018-10-30 | 2022-02-22 | 江苏和成显示科技有限公司 | Liquid crystal composition and display device thereof |
CN111117646B (en) * | 2018-10-30 | 2023-01-10 | 江苏和成显示科技有限公司 | Liquid crystal composition and display device thereof |
CN111117652B (en) * | 2018-10-30 | 2023-03-31 | 江苏和成显示科技有限公司 | Liquid crystal composition and display device thereof |
CN109370613B (en) * | 2018-12-24 | 2020-11-03 | 石家庄晶奥量新材料有限公司 | Liquid crystal composition and application thereof |
CN112300811B (en) * | 2019-08-01 | 2022-07-15 | 江苏和成显示科技有限公司 | Liquid crystal composition and liquid crystal display device |
CN112300810B (en) * | 2019-08-01 | 2022-07-19 | 江苏和成显示科技有限公司 | Liquid crystal composition and liquid crystal display device |
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